Molybdenum complexes of hydrazido- and diazenido-ligands derived from thio- and dithio-carbazates

Mattes, R.; Scholand, Heinz; Mikloweit, Ulrich; Schrenk, V.

doi:10.1107/s0108767387081108

Cited by 2 publications

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References 2 publications

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“…The two MoO bond distances (1.724(7) and 1.730(7) Å for 1b and 1.721(6) Å for 4 ) are similar to those (1.70−1.72 Å) of the reported dioxomolybdenum(VI) complexes having one or two thiolate ligands, e.g. Mo VI O 2 (mercaptoquinolato) 2 , Mo VI O 2 [NMe 2 C 2 H 4 N(C 2 H 4 S) 2 ], Mo VI O 2 (S,N-cys-OMe) 2 , Mo VI O 2 [(SC 2 H 4 NMe) 2 C 2 H 4 ], Mo VI O 2 [(SCH 2 ) 2 py](OSC 4 H 8 ), Mo VI O 2 (SCMe 2 CH 2 NHMe) 2 , Mo VI O 2 (NSC 6 H 12 O 2 ) 2 , Mo VI O 2 (S 2 CNR 2 ) 2 (R = Et, iPr), , and Mo VI O 2 (dttd) …”

Section: Resultssupporting

confidence: 72%

Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoreductase: Synthesis, Structures, and Properties of Q₂[Mo^VIO₂(1,2-benzenedithiolato)₂] (Q = NEt₄, PPh₄) and Related Complexes

et al. 1996

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Three cis-dioxomolybdenum(VI) complexes with dithiolene-like benzenedithiolate ligands, Q2[MoVIO2(1,2-benzenedithiolato)2] (Q = NEt4 (1a), PPh4 (1b)), [MoVIO2(3-triphenylsilyl-1,2-benzenedithiolato)2]2- (2), and [MoVIO2(4-methyl-1,2-benzenedithiolato)2]2- (3), were synthesized as models of oxidized sulfite oxidase and compared with the structure of (PPh4)2[MoVIO2(S2C2(CN)2)2]·2MeOH (4). The crystal data for 1b, chemical formula C60H48O2P2S4Mo, are a = 13.938(6) Å, b = 16.65(1) Å, c = 22.645(5) Å, β = 103.81(2)°, V = 5104(5) Å3, Z = 4, and space group P21/c and the data for 4·2MeOH, chemical formula C58H48O2P2S4Mo, are a = 20.273(3) Å, b = 15.632(5) Å, c = 17.685(4) Å, V = 5604(3) Å3, Z = 4, and space group Pbcn. 1b and 4 have a slightly distorted octahedral structure with two long MoS bonds (2.588(3) Å and 2.608(3) Å for 1b and 2.635(2) Å for 4) trans to each of the MoO groups and with two short MoS bonds (2.417(3) Å and 2.434(3) Å for 1b and 2.440(2) for 4) cis to them. The short SC bond distances of the thiolate trans to the MoO groups in 4 suggest the presence of partial double bonding at the SC (thioketone-like) bond, which contributes to the stabilization of the dioxomolybdenum(VI) species by weakening π-bonding in the MoS bonds trans to the MoO groups. The electron-donating or -withdrawing substituents, e.g. 4-CH3 or 3-SiPh3, on the 1,2-benzenedithiolate Mo(VI) complexes accelerate or retard its oxo-transfer reaction, respectively. The formation of any binuclear Mo(V) complex does not occur in the reaction between [MoVIO2(1,2-benzenedithiolato)2]2- and [MoIVO(1,2-benzenedithiolato)2]2- when the cis-dioxomolybdenum(VI) complex is reduced by triphenylphosphine or benzoin.

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Section: Resultssupporting

confidence: 72%

Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoreductase: Synthesis, Structures, and Properties of Q₂[Mo^VIO₂(1,2-benzenedithiolato)₂] (Q = NEt₄, PPh₄) and Related Complexes

et al. 1996

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“…There are considerable variations in the Mo−S (thiolate) bond distances and Mo−S−Mo angles within the series ( 1 − 4 ). The large Mo−S (thiolate) bond distances ranging from 2.428(1) to 2.484(1) Å are not unprecedented, but much larger than Mo−S (thiolate) bond distances in synthetic complexes reported earlier. 12c,21b The average Mo−S (thiolate) bond distances are 2.473 ( 1 ), 2.457 ( 2 ), 2.458 ( 3 ), and 2.449 Å ( 4 ). The longest bond distance occurs in the case of 1 , explaining the fact that complex 1 is the most unstable one toward thiol dissociation.…”

Section: Resultsmentioning

confidence: 81%

Desoxo Molybdenum(IV) and Tungsten(IV) Bis(dithiolene) Complexes: Monomer−Dimer Interconversion Involving Reversible Thiol Bridge Formation

et al. 2007

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Two series of thiol-bridged dimeric desoxo molybdenum(IV) and tungsten(IV) bis(dithiolene) complexes, [Et(4)N](2)[M(IV)(2)(SR)(2)(mnt)(4)] [M = Mo, R = (1) -Ph, (2) -CH(2)Ph, (3) -CH(2)CH(3), (4) -CH(2)CH(2)OH; M = W, R = (1a) -Ph, (2a) -CH(2)Ph, (3a) -CH(2)CH(3), (4a) -CH(2)CH(2)OH] and one monomeric desoxo complex, [Et(4)N](2)[WIV(SPh)(2)(mnt)(2)] (5a) are reported. These complexes are diamagnetic, and crystal structures of each of the complex (except 5a) exhibits a dimeric {M(IV)(2)(SR)(2)} core without any metal-metal bond where each metal atom possesses hexa coordination. The M-SR distance ranges from 2.437 to 2.484 Angstrom in molybdenum complexes and from 2.418 to 2.469 Angstrom in tungsten complexes. These complexes display Mo-S(R)-Mo angles ranging from 92.84 degrees to 96.20 degrees in the case of 1-4 and W-S(R)-W angles ranging from 91.20 degrees to 96.25 degrees in the case of 1a-4a. Interestingly, both the series of Mo(IV) and W(IV) dimeric complexes respond to an unprecedented interconversion between the dimer and the corresponding hexacoordinated monomer upon change of pH. This pH-dependent interconversion establishes the fact that even the pentacoordinated Mo(IV) and W(IV) bis(dithiolene) moieties are forced to dimerize; these can easily be reverted back to the corresponding monomeric complex, reflecting the utility of dithiolene ligand in stabilizing the Mo(IV)/W(IV) moiety in synthesized complexes similar to the active sites present in native proteins.

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Molybdenum complexes of hydrazido- and diazenido-ligands derived from thio- and dithio-carbazates

Cited by 2 publications

References 2 publications

Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoreductase: Synthesis, Structures, and Properties of Q₂[Mo^VIO₂(1,2-benzenedithiolato)₂] (Q = NEt₄, PPh₄) and Related Complexes

Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoreductase: Synthesis, Structures, and Properties of Q₂[Mo^VIO₂(1,2-benzenedithiolato)₂] (Q = NEt₄, PPh₄) and Related Complexes

Desoxo Molybdenum(IV) and Tungsten(IV) Bis(dithiolene) Complexes: Monomer−Dimer Interconversion Involving Reversible Thiol Bridge Formation

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Molybdenum complexes of hydrazido- and diazenido-ligands derived from thio- and dithio-carbazates

Cited by 2 publications

References 2 publications

Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoreductase: Synthesis, Structures, and Properties of Q2[MoVIO2(1,2-benzenedithiolato)2] (Q = NEt4, PPh4) and Related Complexes

Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoreductase: Synthesis, Structures, and Properties of Q2[MoVIO2(1,2-benzenedithiolato)2] (Q = NEt4, PPh4) and Related Complexes

Desoxo Molybdenum(IV) and Tungsten(IV) Bis(dithiolene) Complexes: Monomer−Dimer Interconversion Involving Reversible Thiol Bridge Formation

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Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoreductase: Synthesis, Structures, and Properties of Q₂[Mo^VIO₂(1,2-benzenedithiolato)₂] (Q = NEt₄, PPh₄) and Related Complexes

Trans Influence of Oxo and Dithiolene Coordination in Oxidized Models of Molybdenum Oxidoreductase: Synthesis, Structures, and Properties of Q₂[Mo^VIO₂(1,2-benzenedithiolato)₂] (Q = NEt₄, PPh₄) and Related Complexes