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Logo of nihpaAbout Author manuscriptsSubmit a manuscriptHHS Public Access; Author Manuscript; Accepted for publication in peer reviewed journal;
 
J Am Chem Soc. Author manuscript; available in PMC 2010 September 9.
Published in final edited form as:
PMCID: PMC2747384
NIHMSID: NIHMS138810

Alkylation of Dinitrogen in [(HIPTNCH2CH2)3N]Mo Complexes (HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3)

Abstract

In this paper we explore the ethylation of dinitrogen (employing [Et3O][BArf4]; Arf = 3,5-(CF3)2C6H3) in [HIPTN3N]Mo (Mo) complexes ([HIPTN3N]3- = [N(CH2CH2NHIPT)3]3-; HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3) with the objective of developing a catalytic cycle for the conversion of dinitrogen into triethylamine. A number of possible intermediates in a hypothetical catalytic cycle have been isolated and characterized; they are MoN=NEt, [Mo=NNEt2][BArf4], Mo=NNEt2, [Mo=NEt][BArf4], Mo=NEt, MoNEt2, and [Mo(NEt3)][BArf4]. Except for MoNEt2, all compounds were synthesized from other proposed intermediates in a hypothetical catalytic reaction. All alkylated species are significantly more stable than their protonated counterparts, especially the Mo(V) species, Mo=NNEt2 and Mo=NEt. The tendency for both Mo=NNEt2 and Mo=NEt to be readily oxidized by [Et3O][BArf4] (as well as by [H(Et2O)2][BArf4], [Mo=NNH2][BArf4], and [Mo=NH][BArf4]) suggest that their alkylation is unlikely to be part of a catalytic cycle. All efforts to generate NEt3 in several stoichiometric or catalytic runs employing MoN2 and Mo[equivalent]N as starting materials were unsuccessful, in part because of the slow speed of most alkylations relative to protonations. In related chemistry that employs a ligand containing 3,5-(4-t-BuC6H4)2C6H3 amido substituents alkylations were much faster, but a preliminary exploration revealed no evidence of catalytic formation of triethylamine.

Introduction

Ever since the discovery of the first transition metal dinitrogen complex, [Ru(NH3)5(N2)]2+,1 scientists have been trying to reduce dinitrogen to ammonia or to prepare organic compounds from dinitrogen under mild conditions. Although the groups of Chatt and Hidai made significant advances toward the catalytic reduction of dinitrogen to ammonia,2-9 no catalytic reduction under mild conditions was achieved. Chatt proposed that coordination of dinitrogen to the appropriate single metal could activate it toward addition of the first proton or electron and that subsequent alternating addition of a proton and an electron would result in formation of two equivalents of ammonia.

Two systems are known in which dinitrogen is reduced under mild conditions. The first is one in which dinitrogen is reduced catalytically to a ~10:1 mixture of hydrazine and ammonia in methanol employing a relatively strong reducing agent such as sodium amalgam.10 The reaction requires molybdenum and is catalytic with respect to it. Hydrazine is the primary product, with ammonia being formed through a metal-catalyzed disproportionation of hydrazine to dinitrogen and ammonia. Shilov proposed that dinitrogen is bound and reduced to hydrazine between two metal centers.

The second system catalytically reduces dinitrogen to ammonia as the primary product at a molybdenum center in a complex that contains the [HIPTN3N]3- ligand, where HIPT = 3,5-(2,4,6-i-Pr3C6H2)2C6H3 (HexaIsoPropylTerphenyl; see Figure 1).11-18 The [HIPTN3N]3- ligand discourages bimetallic chemistry by sterically protecting the metal coordination site, and also provides increased solubility of Mo complexes in nonpolar solvents. The proposed catalytic reduction of dinitrogen to ammonia that involves [HIPTN3N]Mo complexes is shown in Figure 2 (R = H; [HIPTN3N]Mo = Mo). The oxidation states of Mo in the system range from Mo(III) to Mo(VI). Eight of these intermediates have been prepared and crystallographically characterized; they are MoN2, [MoN2]-, Mo-N=NH, [Mo-N=NH2]+, Mo[equivalent]N, [Mo[equivalent]NH]+, [Mo(NH3)]+, and Mo(NH3). All hypothetical compounds that could not be observed and/or isolated were Mo(V) species, e.g., Mo=N-NH2 (not observed) and Mo=NH (observed, but not isolable). Calculations by Reiher and his group on complexes with the full [HIPTN3N]3- ligand set are consistent with the proposed catalytic scheme.19-21 Turnover employing CrCp*2 as the reducing agent and [2,6-Lut][BArf4] (Arf = 3,5-(CF3)2C6H3) as the proton source in heptane is limited to approximately four equivalents of dinitrogen out of a possible six, as a consequence, it is proposed, of the [HIPTN3N]3- ligand being removed from the metal under catalytic conditions. The only other product of the catalytic reduction is dihydrogen.

Figure 1
Drawing of MoN2.
Figure 2
Possible intermediates in the reduction of dinitrogen to ammonia or a trialkylamine at a Mo center through the stepwise addition of R+ (R = H or alkyl, respectively) and electrons.

We became interested in alkylation of dinitrogen and its derivatives in the [HIPTN3N]Mo system for two reasons. First, alkylated dinitrogen and related ligands are likely to be much more robust than their protonated counterparts, a result that might lead to a more detailed understanding of the catalytic reduction of dinitrogen to ammonia. Second, trialkylamines might be synthesized directly from dinitrogen via an analogous set of intermediates to that proposed for reduction to ammonia (Figure 2; R = alkyl). Transition metal-mediated reduction of dinitrogen to form amines under homogeneous catalysis conditions has been reported by Hidai22 and by Mori.23 Both processes require alkali metals as reducing agents and mechanistic details are unknown. Although alkylations of dinitrogen and reduced dinitrogen fragments have been explored in the chemistry of relatively low oxidation state Mo and W dinitrogen complexes,2,5 similar alkylations of relatively high oxidation state molybdenum-based triamidoamine complexes has been investigated only sporadically.24-26 In this paper we explore the possibility that triethylamine might be prepared catalytically in the [HIPTN3N]Mo system.

Results and Discussion

Synthesis of [Et3O][BArf4]

The proton source that was chosen for the catalytic reduction of dinitrogen by [HIPTN3N]Mo catalysts was [2,6-Lut][BArf4] (2,6-Lut = 2,6-dimethylpyridinium). Since [2,6-Lut][BArf4] is relatively insoluble in heptane (the reaction solvent), the direct reduction of protons to H2 by CrCp*2, the reducing agent that is slowly added to the mixture, is minimized. Alkylating agents that contain the [BArf4] anion would be most desirable as they would perturb the system minimally. Therefore turned to the possibility of employing [R3O][BArf4] reagents. All attempts to prepare [Me3O][BArf4] by treating commercially available [Me3O][BF4] with Na[BArf4] under various conditions yielded only complex mixtures. [Et3O][B(C6F5)4] has been mentioned briefly in the literature, although experimental details of its synthesis were not provided.27 The reaction between [Et3O][BF4] and 1.05 equiv of Na[BArf4] proceeded smoothly in diethyl ether over a period of three days to give [Et3O][BArf4] in yields of 90 to 95% as a white solid. [Et3O][BArf4] became the reagent of choice for exploring dinitrogen alkylation reactions.

Synthesis of MoN=NEt

The first plausible intermediate in a hypothetical catalytic alkylation that begins with MoN2 is Mo-N=NEt (3 in Figure 2; R = Et). Diamagnetic MoN=NEt is accessible through reduction of MoCl with excess Na sand under an atmosphere of dry N2 in THF to give [MoN2]- in situ, followed by addition of [Et3O][BArf4] in diethyl ether; MoN=NEt prepared in this manner can be isolated in a moderate yield (42%). The yield of MoN=NEt is higher (69%) when [Bu4N][MoN2] is first prepared and purified, and is then treated with [Et3O][BArf4] in ether (equation 1); this is the preferred method. MoN=NEt also is obtained in 54% yield from MoN2, [Et3O][BArf4], and CrCp*2 in benzene at room temperature after two days. After recrystallization from heptane, MoN=NEt was isolated as a pale yellow, crystalline solid.

[Bu4N][MoN2]+[Et3O][BAr4f]MoN=NEt+[Bu4N][BAr4f]+Et2O
(1)

The 1H NMR spectrum of MoN=NEt in C6D6 displays a triplet at 0.87 ppm and a quartet at 3.31 ppm for the ethyl group, as well as the expected resonances for the [HIPTN3N]Mo core. MoN=NEt can be heated to 80 °C for several days in solution with no sign of decomposition. (MoN=NH is known to decompose to MoH under similar conditions.16) The oxidation of MoN=NEt is fully reversible in PhF (0.1 M [Bu4N][BArf4]; E½ = - 0.18 V; vs. Fc/Fc+) at scan rates between 50 and 700 mV/s (Table 1; Figure 3); the oxidized species is assigned as [MoN=NEt]+. In contrast, oxidation of MoN=NH begins near 0 V but is irreversible.17 Attempts to prepare [MoN=NEt][BArf4] through oxidation of MoN=NEt with [Fc][BArf4] (Fc = FeCp2) or silver salts such as Ag[BArf4] in benzene, diethyl ether, or methylene chloride have been unsuccessful; only immediate decomposition to unidentified species was observed.

Figure 3
Cyclic voltammograms of MoN=NEt in PhF (0.1 M [Bu4N][BArf4] vs. FeCp2/[FeCp2]+).
Table 1
Electrochemical properties of selected protonated and alkylated Mo species.a

Two plausible products in a reaction between MoN2 and [Et3O][BArf4] are [MoN=NEt][BArf4] (2 in Figure 2; R = Et) or a species in which an amido nitrogen is alkylated. The latter would be analogous to an unstable and potentially important intermediate observed when MoN2 is treated with [LutH][BArf4] in fluorobenzene,17 in which an amido nitrogen has been protonated. However, under a variety of conditions (solvent, temperature, stoichiometry) no significant amounts (<10%) of any identifiable alkylated species were formed. Since alkylation of an amido nitrogen is not likely to be reversible, the synthesis of MoN=NEt from MoN2, [Et3O][BArf4], and CrCp*2 in benzene at room temperature noted above must proceed either through formation first of a small amount of [MoN=NEt]+ (followed by reduction) or a small amount of [MoN2]- (followed by alkylation).

Synthesis and reduction of [Mo=NNEt2][BArf4]

Alkylation of MoN=NEt with 1 equiv of [Et3O][BArf4] in CH2Cl2 afforded diamagnetic [Mo=NNEt2][BArf4] as an orange solid in 89% isolated yield (equation 2). According to 1H

MoN=NEt+[Et3O][BAr4f][Mo=NNEt2][BAr4f]+Et2O
(2)

NMR spectroscopy of the reaction mixture, the conversion proceeds without formation of any significant side products. The reaction is complete within 10 - 15 minutes at initial concentrations of 0.047 M in MoN=NEt and [Et3O][BArf4], and within 1 h at initial concentrations of 0.024 M of each. Disappearance of the proton resonances for [Et3O][BArf4] were monitored by 1H NMR in order to obtain a second order rate constant of k2 = 0.23 L·mol−1s−1. The cyclic voltammogram of [Mo=NNEt2][BArf4] in PhF (0.1 M [Bu4N][BArf4]) at a scan rate of 50 mV/s reveals an irreversible reduction at −1.87 V (Ipc; E½ = −1.76 V; vs. Fc/Fc+) which we assign to the [Mo=NNEt2]+/0 couple. This couple is shifted by about ~200–300 mV compared to the [Mo=NNH2]+/0 couple (Table 1).17 Like most of the other Mo compounds described here, [Mo=NNEt2][BArf4] is highly soluble even in pentane, and X-ray quality crystals could not be obtained.

Reduction of [Mo=NNEt2][BArf4] with 1 equiv of CrCp*2 in benzene yielded [CrCp*2][BArf4] and a red, paramagnetic species in ~90% yield according to 1H NMR spectroscopy of the reaction mixture (equation 3). This species is tentatively assigned as the

[Mo=NNEt2][BAr4f]+CrCp2Mo=NNEt2+[CrCp2][BAr4f]
(3)

neutral Mo(V) hydrazido complex, Mo=NNEt2; Mo=NNEt2 is much more stable than Mo=NNH2, which cannot be observed upon attempts to generate it in situ.17 The 1H NMR spectrum of Mo=NNEt2 displays only broad peaks in the diamagnetic region and no characteristic paramagnetically shifted resonances. Attempts to obtain analytically pure material have failed so far, in part because traces of CrCp*2 and [CrCp*2][BArf4] are present, but also because Mo=NNEt2 decomposes slowly in solution over a period of days. Attempts to alkylate Mo=NNEt2 with [Et3O][BArf4] (5 → 6 in Figure 2) resulted only in one electron oxidation of Mo=NNEt2 to reform [Mo=NNEt2][BArf4] in 90–95% yield and butane, which was observed by 1H NMR spectroscopy of the volatile products. As the electrochemical potentials suggest, [Mo=NNH2][BArf4] should oxidize Mo=NNEt2. It does so readily (equation 4). Mo=NNEt2 is also oxidized by [H(OEt2)2][BArf4] in C6D6 and CD2Cl2 in virtually 100% yield.

Mo=NNEt2+[Mo=NNH2][BAr4f][Mo=NNEt2][BAr4f]+Mo=NNH2
(4)

Synthesis of [Mo=NEt][BArf4] and Mo=NEt

Treatment of Mo[equivalent]N with 1 equiv of [Et3O][BArf4] in CH2Cl2 cleanly afforded diamagnetic [Mo=NEt][BArf4] in high yields (up to 93%) as the only product (equation 5). The reaction required about 13 h to go to completion at initial concentrations of 0.047 M.

MoN+[Et3O][BAr4f][Mo=NEt][BAr4f]+Et2O
(5)

[Mo=NEt][BArf4] was isolated as an orange solid. The high solubility of [Mo=NEt][BArf4] in all common solvents, and therefore failure to obtain single crystals suitable for an X-ray study, again prevented structural elucidation. The electrochemistry of [Mo=NEt][BArf4] is comparable to that observed for [Mo=NNEt2][BArf4]. An irreversible reduction is observed at −1.82 V at a scan rate of 50 mV/s (Ipc; E½ = −1.64 V; vs. Fc/Fc+; recorded in PhF and 0.1 M [Bu4N][BArf4]); we assign this reduction to the [Mo=NEt]+/0 couple.

In spite of the irreversible [Mo=NEt]+/0 couple observed in the CV of [Mo=NEt][BArf4], [Mo=NEt][BArf4] can be reduced with 1 equiv of CrCp*2 in benzene to give analytically pure Mo=NEt in virtually 100% yield (equation 6). Mo=NEt is stable both in the solid state

[Mo=NEt][BAr4f]+CrCp2Mo=NEt+[CrCp2][BAr4f]
(6)

and in solution over a period of several weeks at room temperature. The stability of Mo=NEt contrasts with the instability of Mo=NH,17 which is prone to decomposition in the absence of excess reducing agent to form Mo[equivalent]N and [Mo(NH3)]+. As expected for a paramagnetic Mo(V) d1 species, the 1H NMR Spectrum of Mo=NEt shows only broad resonances in the diamagnetic region. No characteristic, paramagnetically shifted resonances for either the ethylene backbone or the ethyl protons could be observed readily at room temperature. The electrochemical oxidation of Mo=NEt to [Mo=NEt]+ is fully reversible in PhF (E½ = −1.64 V; vs. Fc/Fc+; 0.1 M [Bu4N][BArf4], Table 1). We cannot explain why the reduction of [Mo=NEt][BArf4] is irreversible ((vide supra), while the oxidation of Mo=NEt is reversible.

The reactivity of Mo=NEt towards protonation and alkylation is comparable to that observed for Mo=NNEt2 described above. The reaction between Mo=NEt and 1 equiv of [Et3O][BArf4] in various solvents at various temperatures only led to clean oxidation of Mo=NEt to [Mo=NEt][BArf4] and formation of butane (by proton NMR; not quantitated). No evidence for formation of [MoNEt2][BArf4] was obtained. Addition of [H(OEt2)2][BArf4] to Mo=NEt in C6D6 and CD2Cl2 also led simply to oxidation of Mo=NEt to [Mo=NEt][BArf4]. As expected on the basis of electrochemical potentials (Table 1), Mo=NEt readily reduces [Mo=NH][BArf4] in benzene.

Synthesis of cationic [Mo(amine)]+ complexes

We turned to reactions between MoCl and Na[BAr4] (Ar = Ph, Arf) in the presence of NR3, R2NH, or RNH2 (R = Me, Et) in order to determine whether the crowded HIPT system would allow alkyl amines to coordinate to the metal, just as ammonia does.

[Mo(EtNH2)][BArf4] was isolated as a red-brown, crystalline solid in good yield (75%) as shown in equation 7 (amine = EtNH2). Its 1H NMR spectrum displays paramagentically shifted resonances for the ethylene backbone at -16.6 ppm and -98.9 ppm. Reduction of

MoCl+Na[BAr4f]+amine[Mo(amine)][BAr4f]+NaCl
(7)

[Mo(EtNH2)][BArf4] with 1 equiv of CrCp*2 in C6D6 under an atmosphere of N2 afforded MoN2, [CrCp*2][BArf4], and free EtNH2 in less than 15 minutes. The complete exchange of the ethylamine ligand in presumed intermediate Mo(EtNH2) by dinitrogen contrasts with what is found for the reaction between Mo(NH3) and N2, a reaction for which Keq = 1.16(6) in benzene at 22 °C.17 Whether the reaction between Mo(EtNH2) and dinitrogen is zero order or first order in dinitrogen (as it is for the reaction between Mo(NH3) and N2) is not known. The CV of [Mo(EtNH2)][BArf4] under argon shows a quasireversible reduction couple in PhF (E½ = −1.83 V; 0.1 M [Bu4N][BArf4]; Table 1) that we assign as [Mo(EtNH2)]+/0. Interestingly, even though CrCp*2 is technically not a good enough reducing agent in PhF to accomplish the reduction of [Mo(EtNH2)][BArf4] (E½ = -1.63 V; Table 1), the reduction proceeds quantitatively. Evidently precipitation of [CrCp*2][BArf4] provides the additional driving force to complete the reduction in PhF.12,13,15,17,18 [Mo(MeNH2)][BArf4] and [Mo(Me2NH)][BArf4] could be generated and characterized in situ through 1H NMR spectroscopy of the reaction mixtures by methods analogous to that shown in equation 7

Reactions similar to that shown in equation 7 that involve Et2NH, Et3N, and Me3N did not yield any [Mo(amine)][BArf4] over a period of several days, even at elevated temperatures. We ascribe the failure to produce these [Mo(amine)][BArf4] species by methods analogous to that shown in equation 7 to a failure to form what is proposed to be the required Mo(Cl)(amine) intermediate. We therefore turned to alternative approaches.

A successful synthesis of [Mo(Et2NH)][BArf4] is analogous to the reaction between MoH and [2,6-LutH][B(C6F5)4] to yield [Mo(2,6-LutH)][B(C6F5)4].17 [Et2NH2][BArf4] and [Et3NH][BArf4] were prepared by salt metathesis reactions of Na[BArf4] with either [NEt2H2]Cl or [Et3NH]Cl, respectively, and isolated as white solids in high yields. Treatment of a benzene solution of MoH with 1.1 equiv of [Et2NH2][BArf4] at room temperature smoothly afforded [Mo(Et2NH)][BArf4] within 2 h (equation 8). [Mo(Et2NH)][BArf4] is the sole Mo species present

MoH+[Et2NH2][BAr4f][Mo(Et2NH)][BAr4f]+H2
(8)

at any significant concentration in the crude reaction mixture. [Mo(Et2NH)][BArf4] was isolated as an analytically pure red, crystalline solid in yields up to 84% after recrystallization from pentane. The 1H NMR spectrum of [Mo(Et2NH)][BArf4] in C6D6 features two paramagnetically shifted resonances at −9.8 ppm and −88.3 ppm, similar to those observed for the ethylene backbone protons in [Mo(EtNH2)][BArf4] (vide supra). The reduction of [Mo(Et2NH)][BArf4] with one equivalent of CrCp*2 in C6D6 under an atmosphere of N2 produced [CrCp*2][BArf4], MoN2, and free Et2NH within 15 minutes, as judged by 1H NMR spectroscopy of the reaction mixture. The presumed intermediate (Mo(Et2NH)) was not observed.

All efforts to prepare [Mo(NEt3)][BArf4] in a reaction between MoH and [Et3NH][BArf4] in several solvents (C6H6, CH2Cl2, PhF, NEt3) were not successful, even at temperatures up to 100 °C.

Synthesis and characterization of MoNEt2

Since we could not prepare [MoNEt2][BArf4] through the reaction of Mo=NEt with [Et3O][BArf4] (vide supra), we do not have the option to prepare MoNEt2 through reduction of [MoNEt2]+. Therefore we had to devise an alternative synthesis of MoNEt2.

MoNEt2 was isolated as a green solid in a yield of 54% upon treatment of [Mo(NH3)][BPh4] with LiNEt2 in diethyl ether (equation 9). The reaction had to be conducted in

[Mo(NH3)][BPh4]+LiNEt2MoNEt2+Li[BPh4]+NH3
(9)

the absence of N2, otherwise significant amounts of MoN2 were formed as a side product. In the absence of N2, the conversion proceeded cleanly in 2 h and the 1H NMR spectrum of the crude reaction mixture indicated that MoNEt2 was present in a yield of 90–95%. MoNEt2 is noticeably more stable than NH2 (attempted isolation of which led to the formation of Mo[equivalent]N), and could be stored in the solid-state for several weeks at 30 °C without decomposition. We could not prepare MoNEt2 through substitution of the chloride ligand in MoCl by LiNEt2 or through deprotonation of [Mo(Et2NH)][BArf4] with LiNEt2, Li[N(SiMe3)2], or KO-t-Bu, an approach that was successful for preparing MoNH2.17

The 1H NMR spectrum of MoNEt2 at room temperature features paramagnetically shifted resonances for the ethylene backbone at −6.5 ppm and −39.5 ppm, which is suggestive of a ground-state high-spin d2 Mo configuration or a high-spin/low-spin equilibrium, as found in the related compounds [(RNCH2CH2)3N]MoNMe2 (R = SiMe324 or C6F524,28). The resonances of the ethyl groups are also significantly shifted to −1.0 ppm (NCH2CH3) and −66.6 ppm (NCH2CH3). The temperature-dependence of the four resonances observed in the 1H NMR spectrum of MoNEt2 in the range −70 °C to +80 °C allowed us to determine the spin multiplicity of MoNEt2 in the ground-state. A plot of the chemical shift of each resonance vs. 1/T revealed a linear relationship for all, as expected for a Curie-Weiss paramagnet in solution (Figure 4). The methyl resonances in the diethylamide group were almost independent of T as a consequence of their being further away from Mo than the C2H4 protons in the ligand and the methylene protons in the diethylamide group. Thus, in contrast to the low-spin ground-state d2 configurations found for [(RNCH2CH2)3N]MoNMe2 (R = SiMe324 or C6F524,28), MoNEt2 has a high-spin ground-state d2 configuration.

Figure 4
Plot of the chemical shift of selected resonances in MoNEt2 vs. 1/T.

The second temperature dependent process that is observed in NMR spectra of MoNEt2 is loss of C3 symmetry at low temperature (Figure 5). As the temperature is lowered the ligand is locked into a C3 configuration and the dimethylamido group no longer freely rotates. At 200 K at least nine resonances are observed for the two former ethylene backbone protons.

Figure 5
Part of the temperature-dependent 1H NMR spectrum of MoNEt2.

The cyclic voltammogram of MoNEt2 in PhF (0.1 M [Bu4N][BArf4]) reveals a quasireversible oxidation process at E½ = −0.98 V (vs. Fc/Fc+), as well as an irreversible process at −1.74 V (Ipc; vs. Fc/Fc+; scan rate 50 mV/s; Table 1). We assign the former to the one electron oxidation of MoNEt2 to [MoNEt2]+, while the nature of the latter is not known. Chemical oxidation of MoNEt2 with [Fc][BArf4] in toluene over a period of three days is accompanied by a gradual color change of the deep blue solution to deep red. Ferrocene is formed along with a new species with paramagnetically shifted resonances at −8.2, −21.3, −35.7, and −104.3 ppm. Unfortunately, side products are also formed in minor amounts upon oxidation of MoNEt2, and the identity of the major product, which we propose is [MoNEt2]+, therefore cannot be confirmed.

In order to be able to compare compounds that contain the same dialkylamido ligand, MoNMe2 was prepared through reaction of [Mo(NH3)][BPh4] with LiNMe2 in diethyl ether in the absence of dinitrogen. MoNMe2 was obtained as a dark green solid in a moderate yield (39%). MoNMe2 is significantly less stable than MoNEt2 both in the solid-state and in solution. Decomposition of MoNMe2 to undefined products was observed within 24 h in C6D6 solution and within 5 d in the solid-state. The 1H NMR spectrum of MoNMe2 in C6D6 displays paramagnetically shifted resonances for the ethylene backbone at −3.0 ppm and −40.4 ppm at room temperature, as well as for the amine methyl groups at −28.3 ppm. Variable temperature proton NMR spectra of MoNMe2 in toluene-d8 in a range of −20 °C to +80 °C (Figure 6) are analogous to those obtained for MoNEt2. Therefore, we conclude that MoNMe2 also has a high-spin ground state d2 configuration. A low-spin d2 configuration (e.g., for [(RNCH2CH2)3N]MoNMe2 (R = SiMe324 or C6F524,28) would suggest that the amido ligand is planar, while a high-spin d2 configuration for MoNEt2 and MoNMe2 would suggest that the amido ligand is not planar, i.e., pyramidal. We propose that a planar geometry for a diethylamino or dimethylamido group in MoNEt2 and MoNMe2 must not be possible because of steric interaction with the isopropyl HIPT substituents. It should be noted that the energy difference between high spin and low spin forms of [(RNCH2CH2)3N)MoNMe2] (R = SiMe324 or C6F524,28) is small (~2 kcal/mol), so the steric interaction that is required for the lowest energy state to be high spin instead of low spin need not be dramatic.

Figure 6
Part of the temperature-dependent 1H NMR spectrum of MoNMe2.

Alkylation and Reduction of MoNEt2

Alkylation of MoNEt2 with one equivalent of [Et3O][BArf4] in diethyl ether in the absence of dinitrogen cleanly afforded [Mo(NEt3)][BArf4] as a deep red solid in 61% yield after 20 h (equation 10). This result demonstrates that triethylamine can coordinate to the metal in a

MoNEt2+[Et3O][BAr4f][Mo(NEt3)][BAr4f]+Et2O
(10)

cationic Mo core, a fact that would be necessary for a viable catalytic cycle (11 and 12 in Figure 2). The 1H NMR spectrum of paramagnetic [Mo(NEt3)][BArf4] features characteristic resonances for the ethylene backbone protons at −16.3 ppm and −99.1 ppm, as well as resonances for the amine protons at −2.5 ppm and −10.8 ppm. As expected, reduction of [Mo(NEt3)][BArf4] with CrCp*2 in C6D6 under an atmosphere of N2 was accompanied by precipitation of yellow [CrCp*2][BArf4] and formation of MoN2, as judged by 1H NMR spectroscopy of the reaction mixture. Therefore, if [Mo(NEt3)][BArf4] could be formed under catalytic conditions, it would be reduced under dinitrogen to yield triethylamine and MoN2, thus completing the catalytic cycle.

The [DTBTN3N]Mo system

The [HIPTN3N]Mo system appears to be well-suited for the addition of protons and electrons to dinitrogen and NxHy ligands,29 but for steric reasons not for addition of ethyl groups and electrons. Therefore, smaller terphenyl substituents might lead to faster alkylation rates and still relatively stable intermediates. For example, the [DTBTN3N]3- ligand (DTBT = 3,5-(4-t-BuC6H4)2C6H3), which is a sterically less demanding terphenyl analogue of the HIPT system, is known.30 Its complexes are also known to form diazenido derivitives, e.g., [(DTBTN3N)MoN2]- and [DTBTN3N]MoN=NSiMe3.26 Therefore we reasoned that the [DTBTN3N]3- ligand might solve some of the problems associated with the alkylation chemistry of [HIPTN3N]Mo species.

[DTBTN3N]Mo[equivalent]N was synthesized through a reaction between [DTBTN3N]MoCl and 2 equiv of NaN3 in THF at room temperature (equation 11). It was isolated as a yellow powder in a yield of 74%. We could not obtain [DTBTN3N]Mo[equivalent]N through addition of several equivalents of Me3SiN3 to [DTBTN3N]MoCl in toluene at ambient and elevated temperatures.

[DTBTN3N]MoCl+NaN3[DTBTN3N]MoN+NaCl+N2
(11)

Alkylation of [DTBTN3N]Mo[equivalent]N with one equiv of [Et3O][BArf4] in CD2Cl2 was complete within 10 minutes, which is much faster than alkylation of [HIPTN3N]Mo[equivalent]N. Even in benzene, the formation of [(DTBTN3N)Mo=NEt][BArf4] was complete within 15 min. [(DTBTN3N)Mo=NEt][BArf4] was obtained in a 34% yield through crystallization from heptane. Higher yields were thwarted by the poor crystallization behavior of [(DTBTN3N)Mo=NEt][BArf4], which tended to form a deep red oil when concentrated solutions of it in pentane or heptane were cooled. These results suggest that the Mo center in [DTBTN3N]Mo species is much more accessible than in the [HIPTN3N]Mo system, as expected.

Attempts to generate triethylamine

We first attempted to generate triethylamine in the [HIPTN3N]Mo system. MoN2 and Mo[equivalent]N were chosen as starting compounds in experiments that employed [Et3O][BArf4] and CrCp*2. Addition of 7 equiv of [Et3O][BArf4] and 8 equiv of CrCp*2 to a benzene solution of MoN2 or 3.5 equiv of [Et3O][BArf4] and 4.2 equiv of CrCp*2 to a benzene solution of Mo[equivalent]N led to no detectible NEt3 or [Et4N][BArf4] by 1H NMR spectroscopy or gas chromatography. [Et3O][BArf4] is almost insoluble in benzene but is consumed and diethyl ether is formed. The solid residues contained [CrCp*2][BArf4], and either a mixture of Mo=NNEt and [Mo=NNEt2][BArf4], or unreacted Mo[equivalent]N.

Several experiments were conducted in a manner analogous to that employed for the catalytic reduction of dinitrogen to ammonia except the CrCp*2 was added over a period of 10 - 16 hours. In all cases, no NEt3 was formed, as judged by gas chromatography, and the residues contained [CrCp*2][BArf4], Mo[equivalent]N, and undefined decomposition products; no [Et4N][BArf4] was observed by 1H NMR spectroscopy.

Similar experiments were carried out employing [(DTBTN3N)Mo=NEt][BArf4], [Et3O][BArf4], and CrCp*2. Addition of 2.2 equiv of [Et3O][BArf4] and 3.2 equiv of CrCp*2 to a benzene solution of [(DTBTN3N)Mo=NEt][BArf4] was followed by stirring the mixture over a period of 20 h. [(DTBTN3N)Mo=NEt][BArf4], [Et3O][BArf4], and CrCp*2 were all consumed, but no evidence for the formation of NEt3 or [Et4N][BArf4] could be obtained from 1H NMR spectroscopic data, and no (DTBTN3N)Mo derivatives could be identified. Similar results were obtained in attempted catalytic runs using 36 equiv of [Et3O][BArf4] and 48 equiv of CrCp*2 in octane or toluene. Proton NMR analysis of the non-volatile components revealed no [Et4N][BArf4]; only [CrCp*2][BArf4] could be identified. Analysis of the volatiles by gas chromatography revealed a product with a retention time identical to that of NEt3, but the amount was ≤0.2 equiv.

Summary and Conclusions

We have prepared several possible intermediates in a hypothetical catalytic reduction of dinitrogen to triethylamine with (HIPTN3N)Mo species, among them MoN=NEt, [Mo=NNEt2][BArf4], Mo=NNEt2, [Mo=NEt][BArf4], Mo=NEt, MoNEt2, and [MoNEt3][BArf4]. Mo=NNEt2 and Mo=NEt are especially interesting since Mo=NNH2 has not been observed, and Mo=NH loses dihydrogen to give Mo[equivalent]N upon attempted isolation. The protio analog of MoNEt2 (MoNH2) is also unstable with respect to loss of dihydrogen to give Mo[equivalent]N. We were surprised to find that both Mo=NNEt2 and Mo=NEt are oxidized by [Et3O][BArf4] to reform the cationic Mo(VI) species, instead of being alkylated. Mo=NNEt2 is also oxidized by [Mo=NNH2]+ or [H(Et2O)2][BArf4]. Therefore it seems unlikely that it will be possible to complete a catalytic cycle in which Mo=NNEt2 must be alkylated (5 → 6; Figure 2) and Mo=NEt must be alkylated (9 → 10; Figure 2).

We know that reduction of [Mo=NNH2]+ with CrCp*2 gives Mo-N=NH, Mo[equivalent]N, [Mo(NH3)]+, Mo(NH3), and ammonia.17 Mo=NNH2 is proposed to be the first product of reduction of [Mo=NNH2]+, but Mo=NNH2 is then protonated, possibly by [Mo=NNH2]+ in a base-catalyzed proton transfer, to give [Mo=NNH3]+ (and Mo=NNH), and [Mo=NNH3]+ is then reduced by CrCp*2 or some other species in solution (including Mo=NNH2) to give Mo[equivalent]N and ammonia. Therefore Mo=NNH2 and [Mo=NNH3]+ are most likely intermediates, but how they are formed and consumed is unclear.

All efforts to generate NEt3 employing (HIPTN3N)Mo species failed, a result that is consistent with slow alkylations. However, efforts to generate NEt3 in the (DTBTN3N)Mo also have failed so far, or at least NEt3 was not formed catalytically. Nevertheless, sterically less demanding triamidoamine ligands would seem to be more likely to allow formation of NEt3 catalytically in a manner analogous to that proposed for catalytic formation of ammonia.

Unlike protonation of an amido nitrogen in the ligand, alkylation of an amido nitrogen in the ligand would likely be irreversible and probably would lead to dissociation of the amine donor from the metal. Some evidence to support this proposal exists in triamidoamine chemistry of molybdenum.24-26 Alkylation of an amido nitrogen in the [HIPTN3N]3- ligand could be regarded as another potential pitfall in the catalytic formation of triethylamine by a sequence of reactions analogous to those proposed for catalytic formation of ammonia.

Experimental Section

General

Air- and moisture-sensitive compounds were manipulated under an atmosphere of dry N2 or argon by standard Schlenk techniques or in a glove-box using flame- and oven-dried glassware. HPLC grade pentane, benzene, toluene, ether, THF and CH2Cl2 were sparged with dinitrogen, passed through activated alumina, and stored over 4 Å Linde-type molecular sieves prior to use. Heptane, octane, NEt2H and NEt3 were dried by refluxing over molten potassium, vacuum transferred, degassed, and stored over molecular sieves. Gaseous H2NMe, HNMe2, NMe3, and NEt2H were condensed onto sodium sand, stirred over a period of 3 h at −40 °C, and vacuum transferred into the reaction vessel. PhF was dried over CaH2, degassed, and vacuum distilled prior to use. Benzene-d6, toluene-d8, and methylene chloride-d2 were freeze-pump-thaw degassed, and stored over activated molecular sieves for at least two days prior to use. MoCl,16 MoN2,16 [Bu4N][MoN2],16 Mo[equivalent]N,16 [Mo(NH3)][BPh4],16 MoH,17 [Mo=NNH2][BArf4],16 [Mo=NH][BArf4], (DTBTN3N)MoCl,26 [H(OEt2)2][BArf4],31 Na[BArf4], Ag[BArf4],32 CrCp*2,33 and [Fc][BArf4]34 were prepared according to known methods. [Bu4N][BArf4] was prepared by salt metathesis of [Bu4N]Cl with Na[BArf4] in diethyl ether, and recrystallized from CH2Cl2/pentane. [NEt2H2][BArf4] and [NEt3H][BArf4] were synthesized by reaction of NEt2H·HCl and NEt3·HCl with Na[BArf4] in diethyl ether. All other chemicals were obtained commercially, and used without further purification. NMR spectra were recorded on a Bruker Avance 400 spectrometer (1H, 400 MHz; 11B, 128 MHz; 13C, 100 MHz), and VT NMR spectra on Varian Inova 500 spectrometers (1H, 500 MHz). Chemical shifts for 1H NMR spectra were referenced to the residual 1H NMR resonance of the deuterated solvent, those of the 13C NMR spectra to the 13C NMR resonances of the solvent itself, and are reported as parts per million relative to tetramethylsilane. 11B NMR spectra were referenced externally to a solution of B(OH)3 in D2O. Electrochemical measurements were carried out in an argon filled glove-box using a CHI 620C potentiate, 0.1 M [Bu4N][BArf4]/PhF electrolytes, and a standard three-electrode cell assembly with a glassy carbon (3.0 mm dia.) disk working electrode, a platinum wire auxiliary electrode, and a reference electrode consisting of a AgCl-coated silver wire submerged in 0.1 M [Bu4N][BArf4]/PhF electrolyte. All measurements were referenced externally and/or internally with FeCp2. Elemental analyses were performed by Midwest Microlabs, Indianapolis, IN.

[Et3O][BArf4]

A mixture of [Et3O][BF4] (0.15 g, 0.79 mmol) and Na[BArf4] (0.74 g, 0.83 mmol, 1.05 equiv) was stirred in Et2O (10 mL) at room temperature for 3 d. The solvent removed in vacuo. The residue was extracted with CH2Cl2, and the extract was filtered through Celite. Removal of all volatiles afforded [Et3O][BArf4] (0.72 g, 0.74 mmol, 94%) as a white solid, which was washed with pentane and dried in vacuo. A concentrated CH2Cl2 solution was layered with pentane, and cooled to −30 °C to afford analytically pure [Et3O][BArf4]: 1H NMR (400 MHz, CD2Cl2, 297 K) δ 1.61 (t, 9H, CH3), 4.61 (q, 6H, CH2), 7.60 (s, 4H, BArf), 7.60 (s, 8H, BArf); 11B{1H} NMR (128 MHz, CD2Cl2, 297 K) δ −26.0. Anal. Calcd (%) for C38H27BF24O (966.39): C, 47.23; H, 2.82. Found: C, 47.30; H, 2.80.

(HIPTN3N)MoN=NEt

Method A

(HIPTN3N)MoCl (0.15 g, 87.37 μmol) was reduced with sodium sand (38 .1mg, 0.87 mmol, 10 equiv) in THF (4 mL) under an atmosphere of dinitrogen to form [(HIPTN3N)MoN2], as reported in the literature.16 The deep green reaction mixture was filtered through Celite, and the solvents were removed from the filtrate in vacuo. The residue was dissolved in ether (2 mL). The mixture was cooled to −30 °C, and treated dropwise with a solution of [Et3O][BArf4] (84.4 mg, 87.37 μmol, 1 equiv) in ether (2 mL). The reaction was allowed to stir at ambient temperatures over a period of 24 h, and the solvent was subsequently removed under vacuum. The residue was extracted into pentane and filtered through Celite. After removal of all volatiles, the crude product was recrystallized from heptane at −30 °C to afford (HIPTN3N)MoN=NEt (63.8 mg, 36.69 μmol, 42%) as a pale yellow, crystalline solid in several crops: 1H NMR (400 MHz, C6D6, 297 K) δ 0.87 (t, 3H, −NCH2CH3), 1.14 (d, 36H, −CH(CH3)2), 1.22 (d, 36H, −CH(CH3)2), 1.38 (d, 36H, −CH(CH3)2), 2.08 (br t, 6H, −NCH2CH2N−), 2.94 (m, 6H, −CH(CH3)2), 3.32 (m, 12H, −CH(CH3)2), 3.31 (q, 2H, −NCH2CH3), 3.72 (br t, 6H, −NCH2CH2N−), 6.68 (s, 3H, 4,4′,4″-TerH), 7.20 (s, 12H, 3,5,3′,5′,3″,5″-TipH), 7.29 (s, 6H, 2,6,2′,6′,2″,6″-TerH). Anal. Calcd (%) for C116H164MoN6 (1738.52): C, 80.14; H, 9.51; N, 4.83. Found: C, 79.84; H, 9.54; N, 4.85.

Method B (preferred)

An ether solution (8 mL) of [Et3O][BArf4] (0.52 g, 0.54 mmol, 1.05 equiv) was cooled to −30 °C, and treated with solid [Bu4N][(HIPTN3N)MoN2] (1.00 g, 0.51 mmol). A red solution formed within 30 min and was stirred for 20 h. The volatile components were removed in vacuo, and the residue was dried at 50 °C for 3 h. The residue was extracted into pentane and the mixture was filtered through Celite. All volatiles were removed and the crude product was recrystallized from heptane at −30 °C to afford (HIPTN3N)MoN=NEt (0.61 g total, 0.35 mmol, 69%) in several crops.

Method C

A solid mixture of (HIPTN3N)MoN2 (25.0 mg, 14.62 μmol), [Et3O][BArf4] (14.2 mg, 14.62 μmol, 1 equiv), and CrCp*2 (6.2 mg, 14.62 μmol, 1 equiv) was stirred in benzene (7 mL) at RT over a period of two days. All volatile components were removed in vacuo, and the residue was extracted into pentane. The extract was filtered through Celite and the volatiles were removed from the filtrate in vacuo again. The crude product was recrystallized from heptane at −30 °C to afford (HIPTN3N)MoN=NEt (13.7 mg, 7.90 μmol, 54%).

[(HIPTN3N)Mo=NNEt2][BArf4]

An CH2Cl2 solution (3 mL) of (HIPTN3N)MoN=NEt (0.15 g, 86.28 μmol) and [Et3O][BArf4] (83.4 mg, 86.28 μmol, 1 equiv) was stirred at RT for 1 h to give a dark orange solution. Volatiles were removed in vacuo and the solid residue was extracted into pentane. The extracts were filtered through Celite, and the solvents were removed from the filtrate in vacuo. The remaining material was dried at 60 °C under high vacuum to yield [(HIPTN3N)Mo=NNEt2][BArf4] (0.20 g, 76.79 μmol, 89%) as an orange, amorphous solid: 1H NMR (400 MHz, C6D6, 297 K) δ 0.66 (t, 6H, −NCH2CH3), 1.08 (d, 36H, −CH(CH3)2), 1.14 (d, 36H, −CH(CH3)2), 1.42 (d, 36H, −CH(CH3)2), 2.52 (br t, 6H, −NCH2CH2N−), 2.81 (m, 12H, −CH(CH3)2), 2.98 (m, 12H, −CH(CH3)2, −NCH2CH3), 3.77 (br t, 6H, −NCH2CH2N−), 6.89 (s, 9H, 2,4,6,2′,4′,6,′2″,4″,6″-TerH), 7.19 (s, 12H, 3,5,3′,5′,3″,5″-TipH), 7.75 (s, 4H, BArf), 8.45 (s, 8H, BArf). Anal. Calcd (%) for C150H181BF24MoN6 (2630.8): C, 68.48; H, 6.93; N, 3.19. Found: C, 68.73; H, 7.00; N, 3.10.

(HIPTN3N)Mo=NNEt2

A solution of [(HIPTN3N)Mo=NNEt2][BArf4] (0.10 g, 39.53 μmol) in benzene (6 mL) was treated with solid CrCp*2 (12.7 mg, 39.53 μmol, 1 equiv), and stirred for 18 h at RT, during which time a yellow precipitate and a dark red solution formed. All volatiles were removed in vacuo, and the residue was extracted with pentane. The extracts were filtered through a medium porosity frit to yield a deep red filtrate and yellow [CrCp*2][BArf4] (45.9 mg, 38.74 μmol, 98%). The filtrate was brought to dryness to afford a deep red solid. The 1H NMR spectroscopy of the crude reaction mixture indicated the formation of (HIPTN3N)Mo=NNEt2 with a purity of 90%. All attempts to further purify the crude product have been unsuccessful: 1H NMR (400 MHz, C6D6, 297 K) δ 1.22 (br m, 72H, −CH(CH3)2), 1.35 (br s, 36H, −CH(CH3)2), 2.91 (br m, 12H, −CH(CH3)2), 3.18 (br m, 6H, −CH(CH3)2), 7.08 (br s, 12H, 3,5,3′,5′,3″,5″-TipH), all other signals were not observed at RT.

[(HIPTN3N)Mo=NEt][BArf4]

A CH2Cl2 solution (5 mL) of (HIPTN3N)Mo[equivalent]N (0.40 g, 0.24 mmol) and [Et3O][BArf4] (0.23 g, 0.24 mmol, 1 equiv) was stirred at RT for 18 h to give a dark orange solution. Volatiles were removed in vacuo, and the solid residue was extracted with pentane. The extracts were filtered through Celite, and the filtrate was brought to dryness. The remaining material was dried at 60 °C under high vacuum to yield [(HIPTN3N)Mo=NEt][BArf4] (0.57 g, 0.22 mmol, 93%) as an orange, amorphous solid: 1H NMR (400 MHz, CD2Cl2, 297 K) δ 0.62 (t, 3H, −NCH2CH3), 0.85 (d, 36H, −CH(CH3)2), 0.96 (d, 36H, −CH(CH3)2), 1.28 (d, 36H, −CH(CH3)2), 2.51 (m, 12H, −CH(CH3)2), 2.91 (m, 6H, −CH(CH3)2), 3.27 (br t, 6H, −NCH2CH2N−), 3.59 (q, 2H, −NCH2CH3), 4.28 (br t, 6H, −NCH2CH2N−), 6.80 (s, 3H, 4,4′,4″-TerH), 6.84 (s, 6H, 2,6,2′,6,′2″,6″-TerH), 6.98 (s, 12H, 3,5,3′,5′,3″,5″-TipH), 7.56 (s, 4H, BArf), 7.72 (s, 8H, BArf); 1H NMR (400 MHz, C6D6, 297 K): δ = 0.68 (t, 3H, −NCH2CH3), 1.00 (d, 36H, −CH(CH3)2), 1.10 (d, 36H, −CH(CH3)2), 1.34 (d, 36H, −CH(CH3)2), 2.30 (br t, 6H, −NCH2CH2N−), 2.69 (m, 12H, −CH(CH3)2), 2.91 (m, 6H, −CH(CH3)2), 3.64 (m, 8H, −NCH2CH2N−, −NCH2CH3), 6.74 (s, 3H, 4,4′,4″-TerH), 6.82 (s, 6H, 2,6,2′,6,′2″,6″-TerH), 7.14 (s, 12H, 3,5,3′,5′,3″,5″-TipH), 7.69 (s, 4H, BArf), 8.34 (s, 8H, BArf). Anal. Calcd (%) for C148H176BF24MoN5 (2587.73): C, 68.69; H, 6.86; N, 2.71. Found: C, 68.48; H, 6.83; N, 2.88.

(HIPTN3N)Mo=NEt

A solution of [(HIPTN3N)Mo=NEt][BArf4] (0.25 g, 96.61 μmol) in benzene (6 mL) was treated with solid CrCp*2 (31.2 mg, 96.61 μmol, 1 equiv), and the mixture was stirred for 18 h at RT, during which time a yellow precipitate and a dark red solution formed. All volatiles were removed in vacuo at 60 °C, and the residue was extracted with pentane. The extracts were filtered through a medium porosity frit, yielding a deep red filtrate and yellow [CrCp*2][BArf4] (0.11 g, 93.71 μmol, 97%). The filtrate was taken to dryness in vacuo to afford a deep red solid, which was again extracted with pentane. The mixture was filtered through Celite and all volatiles were removed in vacuo to yield (HIPTN3N)Mo=NEt (0.15 g, 85.98 μmol, 89%) as a red, crystalline solid: 1H NMR (400 MHz, C6D6, 297 K) δ 0.91 (br t, 3H, −NCH2CH3), 1.31 (br s, 72H, −CH(CH3)2), 1.40 (br s, 36H, −CH(CH3)2), 2.95 (br m, 12H, −CH(CH3)2), 3.16 (br m, 6H, −CH(CH3)2), 7.06 (br s, 12H, 3,5,3′,5′,3″,5″-TipH); the other signals could not be observed at RT. Anal. Calcd (%) for C116H164MoN5 (1724.52): C, 80.79; H, 9.59; N, 4.06. Found: C, 80.52; H, 9.23; N, 4.29.

Reaction of (HIPTN3N)Mo=NEt with [Et3O][BArf4]

Degassed CD2Cl2 (0.6 mL) was added to a solid mixture of (HIPTN3N)Mo=NEt (20.3 mg, 11.77 μmol) and [Et3O][BArf4] (11.4 mg, 11.77 μmol, 1 equiv). The mixture was thawed to 22 °C, and allowed to react for 1 h, during which time an orange solution formed. The gaseous components of the reaction mixture were vacuum transferred onto frozen and degassed CD2Cl2 (0.6 mL). The 1H NMR spectrum of the volatiles indicated the presence of butane: 1H NMR (400 MHz, CD2Cl2, 297 K) δ 0.88 (t, 6H, CH2CH3), 1.28 (m, 4H, CH2CH3).

[(HIPTN3N)Mo(H2NEt)][BArf4]

Gaseous H2NEt was condensed onto Na sand and the mixture was stirred over a period of 4 h at −30 °C. Two equivalents (57 mL, 0.29 mmol, 95 Torr) were transferred onto a frozen solution of (HIPTN3N)MoCl (0.25 g, 0.15 mmol) and Na[BArf4] (0.15 g, 0.15 mmol, 1.05 equiv) in CH2Cl2 (10 mL). The mixture was allowed to thaw to RT, and was stirred for another 2 h. During this time, the reaction mixture turned red brown in color. The volatiles were removed in vacuo, and the residue was extracted into pentane. The extract was filtered through Celite. The filtrate was reduced in volume and stored at −30 °C to afford [(HIPTN3N)Mo(H2NEt)][BArf4] (0.28 g, 0.11 mmol, 75%) as a red brown, microcrystalline solid. The product was washed with cold pentane and dried in vacuo: 1H NMR (400 MHz, C6D6, 297 K) δ −98.9 (br s, 6H, −NCH2CH2N−), −16.6 (br s, 6H, −NCH2CH2N−), −2.63 (br s, 2H, −H2NCH2CH3), 0.56 (br s, 3H, −NCH2CH3), 1.09 (br s, 36H, −CH(CH3)2), 1.17 (br s, 36H, −CH(CH3)2), 1.40 (br s, 36H, −CH(CH3)2), 2.77 (br m, 12H, −CH(CH3)2), 2.99 (br m, 8H, −CH(CH3)2, −NCH2CH3), 7.25 (br s, 12H, 3,5,3′,5′,3″,5″-TipH), 7.64 (s, 4H, BArf), 8.28 (s, 8H, BArf), 9.73 (br s, TerH); the other signals could not be observed at RT. Anal. Calcd (%) for C148H178BF24MoN5 (2589.74): C, 68.64; H, 6.93; N, 2.70. Found: C, 68.43; H, 6.94; N, 2.80.

[(HIPTN3N)Mo(NEt2H)][BArf4]

A solid mixture of (HIPTN3N)MoH (0.25 g, 0.15 mmol) and [H2NEt2][BArf4] (0.15 g, 0.16 mmol, 1.1 equiv) was treated with benzene (3 mL), and stirred over a period of 2 h at RT. All volatiles were removed in vacuo, the residue extracted into pentane, and filtered through Celite. Removal of all volatile components under high vacuum at 60 °C for 3 h yielded [(HIPTN3N)Mo(NEt2H)][BArf4] (0.33 g, 0.13 mmol, 84%) as a red brown solid: 1H NMR (400 MHz, C6D6, 297 K): δ −88.3 (br s, 6H, −NCH2CH2N−), −9.8 (br s, 6H, −NCH2CH2N−), 0.89 (t, 6H, −NCH2CH3), 1.17 (br s, 72H, −CH(CH3)2), 1.40 (d, 36H, −CH(CH3)2), 2.31 (br s, 4H, −NCH2CH3), 2.90 (br m, 6H, −CH(CH3)2), 3.00 (br m, 12H, −CH(CH3)2, −NCH2CH3), 7.23 (s, 12H, 3,5,3′,5′,3″,5″-TipH), 7.64 (s, 4H, BArf), 8.26 (s, 8H, BArf), 10.6 (br s, TerH); the other signals could not be observed at RT. Anal. Calcd (%) for C150H182BF24MoN5 (2617.8): C, 68.82; H, 7.01; N, 2.68. Found: C, 68.92; H, 7.09; N, 2.72.

(HIPTN3N)MoNEt2

Diethyl ether (10 mL) was freeze-pump-thaw degassed thoroughly and condensed onto a solid mixture of [(HIPTN3N)Mo(NH3)][BPh4] (0.45 g, 0.22 mmol) and LiNEt2 (1.8 mg, 0.22 mmol, 1 equiv). The reaction mixture was allowed to warm to ambient temperature, and was stirred for 2 h. All volatiles were removed in vacuo, and the residue was extracted into pentane under an atmosphere of argon. The mixture was filtered through Celite and the filtrate was brought to dryness in vacuo. The crude reaction product was recrystallized from heptane at −30 °C. (HIPTN3N)MoNEt2 (0.21 g, 0.12 mmol, 54%) was isolated as a green, microcrystalline solid: 1H NMR (500 MHz, toluene-d8, 293 K) δ −66.6 (br s, 6H, −NCH2CH3), −39.5 (br s, 6H, −NCH2CH2N−), −6.5 (br s, 6H, −NCH2CH2N−), −1.97 (br s, TerH), −1.01 (br s, 4H, −NCH2CH3), 1.01 (br s, 36H, −CH(CH3)2), 1.25 (br s, 36H, −CH(CH3)2), 1.40 (d, 36H, −CH(CH3)2), 2.97 (br m, 6H, −CH(CH3)2), 3.05 (br s, 12H, −CH(CH3)2), 7.15 (s, 12H, 3,5,3′,5′,3″,5″-TipH); other resonances could not be observed. Anal. Calcd (%) for C118H169MoN5 (1753.58): C, 80.82; H, 9.71; N, 3.99. Found: C, 81.04; H, 9.54; N, 2.69.

(HIPTN3N)MoNMe2

Diethyl ether (20 mL) was freeze-pump-thaw degassed thoroughly and condensed onto a solid mixture of [(HIPTN3N)Mo(NH3)][BPh4] (0.97 g, 0.48 mmol) and LiNEt2 (24.5 mg, 0.48 mmol, 1 equiv). The reaction mixture was allowed to warm to ambient temperature, and was stirred for 2 h. All volatiles were removed in vacuo, and the residue extracted into heptane/pentane under an atmosphere of argon. The mixture was filtered through Celite and the filtrate was cooled to −30 °C. (HIPTN3N)MoNMe2 (0.32 g, 0.19 mmol, 39%) was isolated as a green solid: 1H NMR (400 MHz, C6D6, 293 K) δ −40.4 (br s, 6H, −NCH2CH2N−), −28.3 (br s, 6H, −NCH3), −3.0 (br s, 6H, −NCH2CH2N−), −0.21 (br s, TerH), 1.21 (br s, 36H, −CH(CH3)2), 1.35 (s, 36H, −CH(CH3)2), 1.47 (d, 36H, −CH(CH3)2), 2.99 (br m, 6H, −CH(CH3)2), 3.12 (br s, 12H, −CH(CH3)2), 7.19 (s, 12H, 3,5,3′,5′,3″,5″-TipH); 7.19 (br s, 3H, -TerH), 26.9 (br s, -TerH). Anal. Calcd (%) for C118H169MoN5 (1753.58): C, 80.82; H, 9.71; N, 3.99. Found: C, 81.04; H, 9.54; N, 3.86.

[(HIPTN3N)Mo(NEt3)][BArf4]

Diethyl ether (1 mL) was condensed onto a solid mixture of (HIPTN3N)MoNEt2 (15.1 mg, 8.55 μmol) and [Et3O][BArf4] (8.3 mg, 8.55 μmol, 1 equiv). The reaction mixture was thawed and stirred for further 16 h at ambient temperature, during which time the solution became deep red. All volatiles were removed in vacuo and the residue was extracted with pentane. The mixture was filtered through Celite and the red filtrate was brought to dryness in vacuo to afford [(HIPTN3N)Mo(NEt3)][BArf4] (13.8 mg, 5.21 μmol, 61%) as a red solid: 1H NMR (400 MHz, C6D6, 297 K) δ −99.1 (br s, 6H, −NCH2CH2N−), −16.3 (br s, 6H, −NCH2CH2N−), −10.8 (br s, 6H, −NCH2CH3), −2.5 (br s, 9H, −NCH2CH3), 1.09 (br s, 36H, −CH(CH3)2), 1.17 (br s, 36H, −CH(CH3)2), 1.40 (d, 36H, −CH(CH3)2), 2.78 (br m, 12H, −CH(CH3)2), 2.99 (br m, 6H, −CH(CH3)2, −NCH2CH3), 7.30 (s, 12H, 3,5,3′,5′,3″,5″-TipH), 7.64 (s, 4H, BArf), 8.27 (s, 8H, BArf), 9.6 (br s, TerH); other resonances could not be observed. Anal. Calcd (%) for C152H186BF24MoN5 (2645.85): C, 69.00; H, 7.09; N, 2.65. Found: C, 68.86; H, 6.69; N, 2.69.

(DTBTN3N)Mo[equivalent]N

THF (4 mL) was added to a solid mixture of (DTBTN3N)MoCl (0.35 g, 0.27 mmol) and NaN3 (34.6 mg, 0.53 mmol, 2 equiv), and the reaction mixture was stirred at RT for 3 d. The volatile components were removed in vacuo, and the solid residue extracted into benzene. The extracts were filtered through Celite, and taken to dryness in vacuo. The remaining material was recrystallized from Et2O/pentane to afford (DTBTN3N)Mo[equivalent]N (33; 0.25 g, 0.20 mmol, 74%) as an orange powder. 1H NMR (400 MHz, C6D6, 297 K): δ 1.23 (s, 54H, −C(CH3)3), 2.25 (br t, 6H, −NCH2CH2N−), 3.61 (br t, 6H, −NCH2CH2N−), 7.27 (d, 12H, 3,5,3′,5,′3″,5″-tBu-C6H4), 7.75 (d, 12H, 2,6,2′,6,′2″,6″-tBu-C6H4), 7.76 (s, 3H, 4,4′,4″-TerH), 8.21 (s, 6H, 2,6,2′,6,′2″,6″-TerH). Anal. Calcd (%) for C84H99MoN5 (1274.66): C, 79.15; H, 7.83; N, 5.49. Found: C, 78.94; H, 7.82; N, 5.67.

[(DTBTN3N)Mo=NEt][BArf4]

A benzene solution (5 mL) of (DTBTN3N)Mo[equivalent]N (0.15 g, 0.11 mmol) was treated with solid [Et3O][BArf4] (11.1 mg, 0.11 mmol, 1 equiv) and the mixture was stirred at RT for 1 h to give a dark red solution. Volatiles were removed in vacuo, and the solid residue was extracted into pentane. The extracts were filtered through Celite, and the filtrate was brought to dryness in vacuo. The remaining material was dried at 60 °C under high vacuum to yield [(DTBTN3N)Mo=NEt][BArf4] (0.21 g, 97.36 μmol, 85%) as a red, amorphous solid. Analytically pure material was obtained by recrystallization from diluted heptane solutions to yield 63.4 mg (29.26 μmol, 26%) of product: 1H NMR (400 MHz, C6D6, 297 K) δ −0.24 (t, 3H, −NCH2CH3), 1.25 (s, 54H, −C(CH3)3), 2.43 (br t, 6H, −NCH2CH2N−), 2.78 (q, 2H, −NCH2CH3), 3.60 (br t, 6H, −NCH2CH2N−), 7.29 (s, 6H, 2,6,2′,6,′2″,6″-TerH), 7.40 (d, 12H, 3,5,3′,5,3″,5″-tBu-C6H4), 7.55 (d, 12H, 2,6,2′,6,′2″,6″-tBu-C6H4), 7.66 (s, 4H, BArf), 7.81 (s, 3H, 4,4′,4″-TerH), 8.40 (s, 8H, BArf). Anal. Calcd (%) for C118H116BF24MoN5 (2166.93): C, 65.40; H, 5.40; N, 3.23. Found: C, 65.29; H, 5.42; N, 3.33.

Acknowledgments

R.R.S. is grateful to the National Institutes of Health (GM 31978) for research support. T.K. is grateful to the German Academic Exchange Service (DAAD) for a fellowship within the Postdoc-Programme, to Dr. Michael Reithofer for helpful discussions, and to Keith M. Wampler for advice on practical aspects of electrochemistry.

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