The bimetallic Ru(2)Pt complex [(Cp*Ru)(2)(mu(2)-NHPh)(mu(2)-H)(mu(3)-C)PtMe(PMe(3))(2)][OTf] (3; Cp* = eta(5)-C(5)Me(5)) containing a planar three-coordinate carbido ligand has been prepared in 93% yield by thermal isomerization of the bridging methylene precursor [(Cp*Ru)(2)Me(mu(3)-NPh)(mu(2)-CH(2))Pt(PMe(3))(2)][OTf] (2) via cleavage of the methylene C-H bonds. Exposure of the carbido complex 3 to carbon monoxide (1 atm) induced coupling of the carbido ligand with the nearby methyl and hydride ligands to produce the diruthenium ethylidene complex [(Cp*Ru)(2)(mu(2)-CHMe)(mu(2)-NHPh)(CO)(2)][OTf] (4) and the known triplatinum complex [Pt(CO)(PMe(3))](3). The crystal structures of 2, 3, and 4 (BPh(4) salt) are reported.
Transition metal imido complexes are an important class of metalÀnitrogen multiply bonded compounds 1À8 that have found many applications in organic synthesis, such as hydroamination of alkynes, 9,10 aziridination of olefins, 11 and nitrene insertion into CÀH bonds. 11,12 Transition metal imido complexes are also widely used as catalysts for the metathesis 13 and polymerization 14 of olefins, where the MdNR multiple bond is an effective ancillary unit that supports electron-deficient metal alkylidene and alkyl species.Recently, considerable attention has been focused on the chemistry of dinuclear bridging imido complexes, which provide unique dinuclear platforms with coordinatively unsaturated metal centers and potentially reactive metalÀnitrogen bonds. 15À41 Early studies by the Bergman and Sharp groups have demonstrated that bridging imido complexes of low-oxidation-state late transition metals display remarkable reactivity, such as the facile single and double insertion of CO into metalÀnitrogen bonds, 23 transfer of a μ-imido ligand to PMe 3 , 24 and interconversion between μ-imido and μ-oxo complexes. 24 Recent efforts by us and others have extended the scope of the imido reactivity in dinuclear systems, such as the alkyne insertion reactions on diruthenium and dirhodium μ-imido complexes, 29,36 CO diamination and redoxcoupled H 2 activation on [Cp*Rh(μ-NTs)] 2 , 37,38 catalytic carbodiimide formation via dinickel μ-imido complexes, 39 and the use of dicopper μ-imido complexes in catalytic CÀH amination reactions. 35 Additionally, bridging imido complexes have also received interest for their relevance to dinitrogen reduction 42À44 and ammonia activation systems. 45,46 In a previous communication, we described the reactions of the diruthenium bridging amido complex [Cp*Ru(μ-NHPh)] 2 (1) 47 with several π-acceptor ligands (i.e., CO, t-BuNC, and CH 2 ). 29 In contrast to the reaction of 1 with PMe 3 , which produces the monomeric amido complex [Cp*Ru(NHPh)(PMe 3 ) 2 ], 47 the reactions of 1 with the above π-acceptor ligands produced the dinuclear bridging imido complexes [(Cp*Ru) 2 (μ-NPh)(μ-L)] (Scheme 1; 2a, L = CO; 2b, L = t-BuNC; 2c, L = CH 2 ). 29 Spectroscopic monitoring of the reaction of 1 with CO revealed that the μ-CO adduct [(Cp*Ru) 2 (μ-NHPh) 2 (μ-CO)] (1a) is rapidly generated upon addition of CO to 1 and cleanly converted into 2a and aniline (Scheme 1), indicating that the imido complex ABSTRACT: [Cp*Ru(μ-NHPh)] 2 (Cp* = η 5 -C 5 Me 5 ) reacted with CO, t-BuNC, Ph 2 SdCH 2 , or Me 3 SiCtCH to give the dinuclear ruthenium bridging imido complexes [(Cp*Ru) 2 (μ-NPh)(μ-L)] (2a, L = CO; 2b, L = t-BuNC; 2c, L = CH 2 ; 2d, L = CCHSiMe 3 ). Protonolysis of 2d with t-BuOH produced the parent vinylidene complex [(Cp*Ru) 2 (μ-NPh)(μ-CCH 2 )] (2e). Treatment of 2e with HOTf or MeOTf afforded the cationic alkylidyne complexes [(Cp*Ru) 2 (μ-NPh)(μ-CR)]OTf (2f, R = Me; 2g, R = Et). Hydride abstraction from 2c with Ph 3 CBF 4 gave the methylidyne complex [(Cp*Ru) 2 (μ-NPh)(μ-CH)]BF 4 (2h). X-ray structures o...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.