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A molybdenum tris-(di-thiol-ene) complex coordinates to three bound cobalt centers in three different ways.

ABSTRACT: The synthesis and structural characterization of the mol-ecular compound (?₃-benzene-1,2-di-thiol-ato)hexa-carbonyl-bis-(?₃-1,1,1,4,4,4-hexafluorobut-2-ene-2,3-dithiolato)tricobaltmolybdenum, [Co₃Mo(C₄F₆S₂)₂(C₆H₄S₂)(CO)₆] or Mo(tfd)₂(bdt)(Co(CO)₂)₃ (tfd is 1,1,1,4,4,4-hexafluorobut-2-ene-2,3-dithiolate and bdt is benzene-1,2-di-thiol-ate), are reported. The structure of the mol-ecule contains the molybdenum tris-(di-thiol-ene) complex Mo(tfd)₂(bdt) coordinated as a multidentate ligand to three cobalt dicarbonyl units. Each of the three cobalt centers is relatively close to molybdenum, with Co?Mo distances of 2.7224?(7), 2.8058?(7), and 2.6320?(6)?Å. Additionally, each of the cobalt centers is bound via main-group donor atoms, but each one in a different way: the first cobalt atom is coordinated by two sulfur atoms from different di-thiol-enes (bdt and tfd). The second cobalt atom is coordinated by one sulfur from one tfd and two olefinic carbons from another tfd. The third cobalt is coordinated by one sulfur from bdt and two sulfurs from tfd. This is, to the best of our knowledge, the first structurally characterized example of a molybdenum (tris-)di-thiol-ene complex that coordinates to cobalt. The F atoms of two of the -CF₃ groups were refined as disordered over two sets of sites with ratios of refined occupancies of 0.703?(7):0.297?(7) and 0.72?(2):0.28?(2).

SUBMITTER: Nguyen N

PROVIDER: S-EPMC6690443 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

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A molybdenum tris-(di-thiol-ene) complex coordinates to three bound cobalt centers in three different ways.

Nguyen Neilson N Lough Alan J AJ Fekl Ulrich U

Acta crystallographica. Section E, Crystallographic communications 20190726 Pt 8

The synthesis and structural characterization of the mol-ecular compound (μ3-benzene-1,2-di-thiol-ato)hexa-carbonyl-bis-(μ3-1,1,1,4,4,4-hexafluorobut-2-ene-2,3-dithiolato)tricobaltmolybdenum, [Co3Mo(C4F6S2)2(C6H4S2)(CO)6] or Mo(tfd)2(bdt)(Co(CO)2)3 (tfd is 1,1,1,4,4,4-hexafluorobut-2-ene-2,3-dithiolate and bdt is benzene-1,2-di-thiol-ate), are ...[more]

PMID: 31417803

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Project description:Two coordination compounds containing tetra-n-butyl-ammonium cations and bis-tfd-chelated molybdenum(IV) [tfd2- = S2C2(CF3)22-] and oxalate (ox2-, C2O42-) in complex anions are reported, namely bis-(tetra-n-butyl-ammonium) bis-(1,1,1,4,4,4-hexa-fluoro-but-2-ene-2,3-di-thiol-ato)oxalatomolybdate(IV)-chloro-form-oxalic acid (1/1/1), (C16H36N)2[Mo(C4F6S2)2(C2O4)]·CHCl3·C2H2O4 or (N n Bu4)2[Mo(tfd)2(ox)]·CHCl3·C2H2O4, and bis-(tetra-n-butyl-ammonium) μ-oxalato-bis-[bis-(1,1,1,4,4,4-hexa-fluoro-but-2-ene-2,3-di-thiol-ato)molybdate(IV)], (C16H36N)2[Mo2(C4F6S2)4(C2O4)] or (N n Bu4)2[(tfd)2Mo(μ-ox)Mo(tfd)2]. They contain a terminal oxalate ligand in the first compound and a bridging oxalate ligand in the second compound. Anion 12- is [Mo(tfd)2(ox)]2- and anion 22-, formally generated by adding a Mo(tfd)2 fragment onto 12-, is [(tfd)2Mo(μ-ox)Mo(tfd)2]2-. The crystalline material containing 12- is (N n Bu4)2-1·CHCl3·oxH2, while the material containing 22- is (N n Bu4)2-2. Anion 22- lies across an inversion centre. The complex anions afford a rare opportunity to compare terminal oxalate with bridging oxalate, coordinated to the same metal fragment, here (tfd)2MoIV. C-O bond-length alternation is observed for the terminal oxalate ligand in 12-: the difference between the C-O bond length involving the metal-coordinating O atom and the C-O bond length involving the uncoordinating O atom is 0.044 (12) Å. This bond-length alternation is significant but is smaller than the bond-length alternation observed for oxalic acid in the co-crystallized oxalic acid in (N n Bu4)2-1·CHCl3·oxH2, where a difference (for C=O versus C-OH) of 0.117 (14) Å was observed. In the bridging oxalate ligand in 22-, the C-O bond lengths are equalized, within the error margin of one bond-length determination (0.006 Å). It is concluded that oxalic acid contains a localized π-system in its carb-oxy-lic acid groups, that the bridging oxalate ligand in 22- contains a delocalized π-system and that the terminal oxalate ligand in 12- contains an only partially localized π-system. In (N n Bu4)2-1·CHCl3·oxH2, the F atoms of two of the -CF3 groups in 12- are disordered over two sets of sites, as are the N and eight of the C atoms of one of the N n Bu4 cations. In (N n Bu4)2-2, the whole of the unique N n Bu4+ cation is disordered over two sets of sites. Also, in (N n Bu4)2-2, a region of disordered electron density was treated with the SQUEEZE routine in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18].

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A molybdenum tris-(di-thiol-ene) complex coordinates to three bound cobalt centers in three different ways.

Publications

A molybdenum tris-(di-thiol-ene) complex coordinates to three bound cobalt centers in three different ways.

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