Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes

Journal Article · Mon Mar 02 00:00:00 EST 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b00302· OSTI ID:1353234

Thompson, Rick; Tran, Ba L.; Ghosh, Soumya; Chen, Chun-Hsing; Pink, Maren; Gao, Xinfeng; Carroll, Patrick J.; Baik, Mu-Hyun; Mindiola, Daniel J.

In this study we enumerate the reactivity for two molecular vanadium nitrido complexes of [(nacnac)V≡N(X)] formulation [nacnac = (Ar)NC(Me)CHC(Me)(Ar)^-, Ar = 2,6-(CHMe₂)₂C₆H₃); X– = OAr (1) and N(4-Me-C₆H₄)₂ (Ntolyl₂) (2)]. Density functional theory calculations and reactivity studies indicate the nitride motif to have nucleophilic character, but where the nitrogen atom can serve as a conduit for electron transfer, thus allowing the reduction of the vanadium(V) metal ion with concurrent oxidation of the incoming substrate. Silane, H₂SiPh₂, readily converts the nitride ligand in 1 into a primary silyl–amide functionality with concomitant two-electron reduction at the vanadium center to form the complex [(nacnac)V{N(H)SiHPh₂}(OAr)] (3). Likewise, addition of the B–H bond in pinacolborane to the nitride moiety in 2 results in formation of the boryl–amide complex [(nacnac)V{N(H)B(pinacol)}(Ntolyl₂)] (4). In addition to spectroscopic data, complexes 3 and 4 were also elucidated structurally by single-crystal X-ray diffraction analysis. One-electron reduction of 1 with 0.5% Na/Hg on a preparative scale allowed for the isolation and structural determination of an asymmetric bimolecular nitride radical anion complex having formula [Na]₂[(nacnac)V(N)(OAr)]₂ (5), in addition to room-temperature solution X-band electron paramagnetic resonance spectroscopic studies.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• OSTI ID: 1353234
• Journal Information: Inorganic Chemistry, Vol. 54, Issue 6; ISSN 0020-1669
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY