Jiutong Chen

Synthesis and structural characterization of Mo2(μ-SC6H4–Cl-p)2(μ-dppm)(CO)6 and [(dppm)(CO)2Mo(μ-SC6H4–Cl-p)2Mo(O)]2(μ-SC6H4–Cl-p)2(μ-O) and electrochemical property of Mo2(μ-SC6H4–Cl-p)2(μ-dppm)(CO)6

Abstract Dimolybdenum(I) compound Mo2(μ-SC6H4–Cl-p)2(μ-dppm)(CO)6 (1), (dppm=(C6H5)2PCH2P(C6H5)2), and a trace unexpected mixed-valence tetranuclear molybdenum compound [(dppm)(CO)2Mo(μ-SC6H4–Cl-p)2Mo(O)]2(μ-SC6H4–Cl-p)2(μ-O) (2) were obtained from the reaction of Mo2(μ-SC6H4–Cl-p)2(CO)8 with dppm in CH2Cl2. The crystal structures of the two compounds have been determined by X-ray diffraction studies. 1: monoclinic, P2(1)/n, a=13.1082(3), b=23.9584(4), c=14.8510(2) A, β=105.865(1)°, V=4486.32(14) A3, Z=4, 9859 unique data, R1=0.0805, wR2=0.1076. 2·CH2Cl2: monoclinic, C2/c, a=22.0955(13), b=19.1563(11), c=25.1981(14) A, β=112.243(1)°, V=9871.9(1) A3, Z=4, 7053 unique data, R1=0.0450, wR2=0.1222. The cyclic voltammetry (CV) measurement for 1 showed a reversible two-electron transfer in a single step.

A mixed tribridging dimolybdenum(I) compound, bis(μ-benzenethiolato-S:S)hexacarbonyl-μ-iodo-dimolybdenum(I)(Mo—Mo)

In the structure of the complex anion of the title compound, (C 16 H 36 N)[Mo 2 I(C 6 H 5 S) 2 (CO) 6 ], two Mo atoms are linked by three bridging ligands (one I and two benzenethiolate), forming an Mo 2 I(C 6 H 5 S) 2 core. The Mo 2 S 2 unit, with a mean Mo-S distance of 2.475(2) A and a mean Mo-S-Mo angle of 71.21(4)°, is approximately planar. Relative to this Mo2S2 unit, the two benzene rings are in a syn configuration. The Mo-I distances are 2.9460 (6) and 2.9599 (6) A, the Mo-Mo distance is 2.8824 (7) A and the Mo-I-Mo angle is 58.43 (2)°.

A dimolybdenum(I) carbonyl compound with thiolate and carboxylate bridges: tetrabutylammonium bis(μ-benzenethiolato-S:S)hexacarbonyl-μ-pivalate-O:O'-dimolybdenum(Mo—Mo)

In the anion of the title compound, (C 16 H 36 N)[Mo 2 -(C 5 H 9 O 2 )(C 6 H 5 S) 2 (CO) 6 ], each Mo atom and three terminal carbonyl groups form a fac-Mo(CO) 3 fragment, and two Mo atoms and two benzenethiolate bridging ligands form a planar Mo2S2 unit, with the two phenyl rings in an anti configuration. The pivalate acts as a conventional μ,η 2 -ligand bridge to two Mo atoms, to form an approximately planar five-membered ring. The two [MoOS 2 (CO) 3 ] octahedra share a common S-S edge.

A Hetero-Tribridged Dinuclear Molybdenum Compound [Bu4N][Mo2(CO)6(p-Cl-C6H4 S)2Br]

The title compound, tetra-n-butylammonium μ-bromo-bis(μ-p-chlorobenzenethiolato)bis(tricarbonylmolybdenum)(Mo-Mo), (C 16 H 36 N)[Mo 2 Br(C 6 H 4 ClS) 2 (CO) 6 ], contains a Bu 4 N + cation and an [Mo 2 (CO) 6 (p-Cl-C 6 H 4 S) 2 Br] - anion. The structure of the anion can be viewed as a cofacial bi-octahedral dimer, in which two fac-Mo(CO) 3 fragments are bridged by two p-Cl-C 6 H 4 S - groups and one Br- ligand. The mean Mo-Br distance is 2.765 (2) A and the Mo-Br-Mo angle is 62.68 (4)°.

A New Dinuclear Molybdenum Compound, (Bu4 N)[Mo2(CO)6(SPh)2(CH2CCH3COO)]

The crystal structure of the title compound, tetrabutylammonium bis(μ-benzenethiolato-S:S)-μ-methacrylato-O:O′-bis(tricarbonylmolybdenum)(Mo—Mo), (C16H36N)[Mo2(C4H5O2)(C6H5S)2(CO)6], shows that it contains a Bu4N+ cation and a dinuclear anion with three bridging ligands, i.e. [Mo2(CO)6(SPh)2(CH2CCH3COO)]−; the α-methacrylate group acts as a bidentate bridging ligand and coordinates two Mo atoms to form a five-membered ring. The Mo—Mo bond distance is 2.9115 (5) A and the O—C—O angle is 125.8 (4)°.