Dinuclear molybdenum cluster-catalyzed radical addition and polymerization reactions by tuning the redox potential of a quadruple bonded Mo2 core.

Modeling of Reversible Chain Transfer Catalyzed Polymerization by Moment Equations Method

A moment equations method was performed to study the Reversible chain Transfer Catalyzed Polymerization (RTCP) of styrene in 80°C. To do this, a kinetic scheme containing conventional free radical polymerization reactions and equilibrium reactions of RTCP was assumed. After obtaining mass balance equations, three moment equations were defined for free and dormant radicals and dead chains. M...

Electronic tuning of Mo2(thioamidate)4 complexes through π-system substituents and cis/trans isomerism.

We report an exploration of the coordination chemistry of a systematic series of cyclic thioamidate ligands with the quadruply-bonded Mo2(4+) core. In addition to the S and N donor atoms that bind to Mo, the ligands utilized in this study have an additional O or S atom in conjugation with the thioamidate π system. The preparation of four new Mo2 complexes is described, and these compounds are c...

Lithium Di- and trimethyl dimolybdenum(II) complexes with Mo-Mo quadruple bonds and bridging methyl groups.

New dimolybdenum complexes of composition [Mo2{μ-Me}2Li(S)}(μ-X)(μ-N^N)2] (3a-3c), where S = THF or Et2O and N^N represents a bidentate aminopyridinate or amidinate ligand that bridges the quadruply bonded molybdenum atoms, were prepared from the reaction of the appropriate [Mo2{μ-O2CMe}2(μ-N^N)2] precursors and LiMe. For complex 3a, X = MeCO2, while in 3b and 3c, X = Me. Solution NMR studies i...

Mixed-ligand complexes of paddlewheel dinuclear molybdenum as hydrodehalogenation catalysts for polyhaloalkanes† †Electronic supplementary information (ESI) available: Experimental details for the synthesis and characterization of Mo2 complexes, kinetic analysis of the reactions, 1H NMR spectra of the catalytic reactions, identification of the products, CV of selected Mo2 complexes, and crystal data for 7a (CCDC 1046579), 9a (CCDC 1046580), 10a (CCDC 1046581), and 11a (CCDC 1046582). CCDC 1046579–1046582. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00721f

A three-coordinate and quadruply bonded Mo-Mo complex.

Reaction of MoCl3(THF)3 with [Me2Si{NLi(Dipp)}2]2 (Dipp = 2,6-i-PrC6H3) afforded a triply bonded dimolybdenum complex 1,2-Mo2Cl2[Me2Si(NDipp)2]2 1, spanned by two Me2Si[N(Dipp)]2 ligands, thus resulting in a syn conformation. The air- and moisture-sensitive compound 1 was characterized by NMR spectroscopic, elemental, and single-crystal X-ray crystallographic analysis. Reduction of 1 by Na/Hg y...