Mononuclear octahedral and dinuclear edge-sharing and face-sharing bioctahedral compounds of molybdenum(III). Electronic control on the extent of metal-metal interaction in the dinuclear systems. An equilibrium, structural, and paramagnetic NMR study

Abstract

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Attachment of a Hydrogen‐Bonding Carboxylate Side Chain to an [FeFe]‐Hydrogenase Model Complex: Influence on the Catalytic Mechanism

“…16 An EPR study of a solution of the dichloride complex in toluene, in the presence of an equivalent amount of the Al(O i Pr) 3 compound, at 80 °C (conditions used for the ATRP of methyl acrylate (MA)5) reveals no change of shape nor intensity over 1 h. The 15‐electron [MoX 3 (PMe 3 ) 3 ] complexes do not show any EPR activity in isotropic solutions at room temperature. However, in spite of their paramagnetism, they display highly shifted and broad but readily visible resonances in the 1 H NMR spectrum 17. The addition of one equivalent of Al(O i Pr) 3 to a solution [MoCl 3 (PMe 3 ) 3 ] in C 6 D 6 at 65 °C for 8 h does not yield any visible change of the solution NMR spectroscopic properties.…”

Anionic Halomolybdate(III) Chemistry. Tetrahydrofuran Loss from [MoX3Y(THF)2]-(X, Y = Cl, Br, I), Preparation and Properties of [Mo3X12]3-(X = Br, I), and Crystal Structure of the Edge-Sharing Trioctahedral [PPh4]3[Mo3I12]

“…) neutral 2-electron donor) mononuclear octahedral MoX 3 L 3 , [1][2][3][4][5][6][7][8][9][10][11] [MoX 4 L 2 ] -, 10,12-14 and [MoX 6 ] 3-, 15,16 dinuclear edge-sharing bioctahedral Mo 2 X 6 L 4 , [17][18][19][20][21][22][23][24] dinuclear face-sharing bioctahedral Mo 2 X 6 L 3 , 22,[25][26][27] [Mo 2 X 7 L 2 ] -, 28,29 and [Mo 2 X 9 ] 3-, [30][31][32][33] and the MoX 3 solids where one-third of the octahedral holes of the closepacked halide substructure are occupied by the metal atoms. 34,35 The occupied octahedral holes are arranged pairwise to give an infinite three-dimensional (for X ) Cl) and monodimensional (for X ) Br) {X 3/2 Mo(µ-X) 3 MoX 3/2 } ∞ structure with localized Mo-Mo bonds.…”

[(Cp*RuCl)2(μ-Cl)2]: Bond-Stretch or Spin-State Isomerism?

“…The validity of the distinction between ªbond-stretchº and ªspin-stateº isomerism is then reexamined in the context of dimetallic clusters. d(CF 2 Cl 2 ) 0, external): d À 136.9 (d, 2 F, J(F,F) 8.4 Hz; F meta ), À 167.7 (tr, 1 F, J(F,F) 20.7 Hz; F para ), À 171.5 (tr, 2 F, J(F,F) 16.8 Hz; F ortho ); 13 Optimization of the structure of the broken-symmetry state of [(CpRuCl) 2 (m-Cl) 2 ] (Cp C 5 H 5 ) does indeed reveal two minima, denoted S 1 and S 2 , depending on the starting geometry. The calculated RuÀRu separations of 2.881 and 3.753 (Table 1) for S 1 and S 2 , respectively, are remarkably similar to those in 1 a and 1 b, as are the other bond lengths and angles.…”