Syntheses and structures of the seven-coordinate molybdenum carbonyl complexes containing both dithiocarbamate and the uninegative nitrogen-tripod ligand

Shiu, Kom-Bei; Lee, Jean Y.; Wang, Yu; Cheng, Ming Chu

doi:10.1021/ic00068a031

Cited by 13 publications

(9 citation statements)

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“…Boron-centered tripodal ligands represent a wide class of compounds that have been extensively studied for their coordination properties with transition-metal and s−p block metal ions. Since the introduction of the hydrotris(pyrazolyl)borates (Tp's) in the 1960s by Trofimenko, various tripodal ligands have been prepared following the same synthetic method . Hydrotris(methimazolyl)borate (Tm) was prepared a few years ago by Reglinski and co-workers, and its donor capabilities rely on the soft environment of three thioxo groups if compared to the hard donor set of the Tp ligand class (three pyrazole nitrogen atoms) .…”

Section: Introductionmentioning

confidence: 99%

Versatile Ligand Behavior of Hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate. Syntheses and Crystal Structures of Cu(I) and Bi(III) Complexes

et al. 2003

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Preparations of copper(I) and bismuth(III) complexes of hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate (Tr(Et,Me)) are described. These complexes have been characterized by means of spectroscopy and microanalysis. Molecular structures of [Cu(Tr(Et,Me))](2) x 2.5CH(3)CN x 0.5H(2)O (3a) and [Bi(Tr(Et,Me))(2)]NO(3) x 2CHCl(3) (4a) have been determined by single-crystal X-ray diffraction. In the centrosymmetric dimeric copper(I) complex, Tr(Et,Me) acts in the k(3)S,S',H:kS' ' coordination mode. The metal is found in a distorted trigonal geometry as the ligand exhibits an "S(3)-inverted" conformation at the boron center so that a weak [B-H.Cu] agostic interaction renders the overall coordination of the (3 + 1) type. On the other hand, in the bismuth complex, Tr(Et,Me) presents the k(3)S,S',S' ' coordination mode and the "S(3)-normal" conformation. The metal is found in a regular octahedral geometry bound by six thioxo groups of two ligands. Species distributions in solution have been studied using electrospray ionization mass spectrometry upon dissolution of 3a and 4a crystals in acetonitrile. Monomeric and polynuclear copper(I) complexes with different M:L ratios are present in solution, while for 4a only the monomeric species is present.

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Section: Introductionmentioning

confidence: 99%

Versatile Ligand Behavior of Hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate. Syntheses and Crystal Structures of Cu(I) and Bi(III) Complexes

et al. 2003

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“…Thus, the Mo−C(50) distance of 1.917(3) Å, with the C(50) atom trans to the N(21) atom, is shorter than the Mo−C(40) distance of 2.039(3) Å; the Mo−N(21) distance is the longer of the three W−N bonds. The steric demands of the Tp* ligand lead to an opening of the OC−M−CO angle in 3 (97.8(1)°) and its structurally related W analogue (97.5°) 57 as compared to the angles typical of complexes with sterically unencumbered scorpionate co-ligands (<75°) …”

Section: Resultsmentioning

confidence: 99%

“…The new synthesis is based on sulfur atom transfer from propylene sulfide to Tp*Mo(S 2 CNEt 2 )(CO) 2 , as described for the W analogue . The dicarbonyl precursor was prepared by modification of a literature method for the synthesis of LMo(S 2 CNEt 2 )(CO) 2 [L = Tp, HB(C 2 H 2 N 3 ) 3 - , PhB(C 2 H 2 N 3 ) 3 - ] from LMoI(CO) 3 and AgS 2 CNEt 2 in acetonitrile . Interestingly, the method reportedly failed to yield 3 when Tp*MoI(CO) 3 was reacted with AgS 2 CNEt 2 .…”

Section: Resultsmentioning

confidence: 99%

Formation of Mono(dithiolene)−Thiocarboxamido Complexes in Reactions of Thio(dithiocarbamato)−Mo/W Complexes and Dimethyl Acetylenedicarboxylate

et al. 2004

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Reactions of TpMS(S(2)CNEt(2)) with dimethyl acetylenedicarboxylate in dichloromethane produce olive green/black TpM{S(2)C(2)(CO(2)Me)(2)}(SCNEt(2)-kappa(2)S,C) (M = Mo (1), W (2); Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate). The seven-coordinate complexes exhibit pseudo-octahedral (1) and distorted pentagonal bipyramidal (2) coordination spheres comprised of tridentate fac-Tp, bidentate dithiolene, and thiocarboxamido-kappa(2)S,C ligands. In the solid state, molecules of 1 exhibit pseudo-C(s)() symmetry, with the thiocarboxamide NEt(2) group in a cleft in the Tp ligand. Molecules of 2 have C(1) symmetry in the solid state; here, the thiocarboxamide unit is orientated along one of the W-S(dithiolene) bonds with its NEt(2) group projecting away from the Tp ligand. Both complexes possess effective C(s)() symmetry in solution. Reaction of TpMoI(CO)(3) with AgS(2)CNEt(2) affords olive green TpMo(S(2)CNEt(2))(CO)(2) (3), which reacts with propylene sulfide in a new synthesis for TpMoS(S(2)CNEt(2)), the starting material for 1. Complex 3 exhibits a distorted pentagonal bipyramidal structure, the axial sites being defined by a Tp nitrogen atom and a carbonyl ligand, the pentagonal plane by the remaining nitrogen and carbonyl donors and the two sulfur atoms of the bidentate dithiocarbamate ligand.

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“…The Mo-N distance is slightly longer (2.344 Á) than that observed (2.25 Á) in seven-coordinated Modi) complex [Mo(CO)2(?/2-(S,S)X?73-Tp)] {(S,S)" = dithiocarbamato, Tp = tris(pyrazolyl)borate} where three nitrogens of the tris(pyrazolyl)borate are coordinated along with a dithiocarbamate ligand. 28 The Mo-C2…”

Section: Resultsmentioning

confidence: 99%

Organometallic Chemistry of Diphosphazanes. 11. Reactions of fac-[Mo(CO)3(MeCN){.eta.2-Ph2PN(Pri)PPh(DMP)}] (DMP = 3,5-Dimethyl-1-Pyrazolyl) with Diphosphazanes and Diphosphinoalkanes and Oxidative Addition with Iodine

Babu¹,

Krishnamurthy²,

Nethaji³

1995

Organometallics

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Syntheses and structures of the seven-coordinate molybdenum carbonyl complexes containing both dithiocarbamate and the uninegative nitrogen-tripod ligand

Cited by 13 publications

References 0 publications

Versatile Ligand Behavior of Hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate. Syntheses and Crystal Structures of Cu(I) and Bi(III) Complexes

Versatile Ligand Behavior of Hydrotris(4-ethyl-3-methyl-5-thioxo-1,2,4-triazolyl)borate. Syntheses and Crystal Structures of Cu(I) and Bi(III) Complexes

Formation of Mono(dithiolene)−Thiocarboxamido Complexes in Reactions of Thio(dithiocarbamato)−Mo/W Complexes and Dimethyl Acetylenedicarboxylate

Organometallic Chemistry of Diphosphazanes. 11. Reactions of fac-[Mo(CO)3(MeCN){.eta.2-Ph2PN(Pri)PPh(DMP)}] (DMP = 3,5-Dimethyl-1-Pyrazolyl) with Diphosphazanes and Diphosphinoalkanes and Oxidative Addition with Iodine

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