The syntheses and structural characterization of the CS2–metal complexes [(η5-C5Me5M)(η2-S2CH2)(η3-S2CH)] (1: M = Mo; 2: M = W), which feature partially and fully reduced CS2, are reported. In addition, the cis and trans isomers of the dimetallic (sulfido)molybdenum complexes [(η5-C5Me5Mo)2(µ-S2CH2S)2] (3-cis and 4-trans) are described. The [Mo2S4] cores of 3-cis and 4-trans represent paddlewheel-like arrays. All the new compounds were characterized in solution by mass spectrometry, IR spectroscopy, and1H and13C NMR spectroscopy. Their structural architectures were established by X-ray crystallographic analysis. Quantum-chemical calculations by DFT methods on the model compounds 1′–4′-trans showed good agreement with the experimentally observed structural parameters. The large HOMO–LUMO (HOMO = highest occupied molecular orbital, LUMO = lowest unoccupied molecular orbital) gaps are consistent with the high thermodynamic stabilities of these complexes. Further, the presence of short metal–metal cross-cluster bonds in the X-ray structures of 3-cis and 4-trans is supported by natural bond order (NBO) calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Sundargopal Ghosh

Department Of Chemistry

Chokkapu Eswara Rao

Kuppusamy Yuvaraj

Kirubakaran Bakthavachalam

IIT Madras is a public technical and research university located in Chennai, Tamil Nadu. Founded in 1959, it is recognised as an Institute of National Importance.

IIT Madras has been ranked as the top engineering institute in India for four years in a row by the National Institutional Ranking Framework of the MHRD

It currently offers undergraduate, postgraduate and research degrees across 16 disciplines in Engineering, Sciences, Humanities and Management. About 596 faculty belonging to science and engineering departments and centres of the Institute are engaged in teaching, research and industrial consultancy.

IIT Madras

European Journal of Inorganic Chemistry

The thermolysis of arachno-1 [(Cp*Ru) 2 (B 3 H 8 )(CS 2 H)] in the presence of tellurium powder yielded a series of ruthenium trithia-borinane complexes: [(Cp*Ru) 2 (η 1 -S)(η 1 -CS){(CH 2 ) 2 S 3 BH}] 2, [(Cp*Ru) 2 (η 1 -S)(η 1 -CS){(CH 2 ) 2 S 3 B(SMe)}] 3, and [(Cp*Ru) 2 (η 1 -S)(η 1 -CS){(CH 2 ) 2 S 3 BH}] 4. Compounds 2-4 were considered as ruthenium trithia-borinane complexes, where the central six-membered ring {C 2 BS 3 } adopted a boat conformation. Compounds 2-4 were similar to our recently reported ruthenium diborinane complex [(Cp*Ru){(η 2 -SCHS)CH 2 S 2 (BH 2 ) 2 }]. Unlike diborinane, where the central six-membered ring {CB 2 S 3 } adopted a chair conformation, compounds 2-4 adopted a boat conformation. In an attempt to convert arachno-1 into a closo or nido cluster, we pyrolyzed it in toluene. Interestingly, the reaction led to the isolation of a capped butterfly cluster, [(Cp*Ru) 2 (B 3 H 5 )(CS 2 H 2 )] 5. All the compounds were characterized by 1 H, 11 B{ 1 H}, and 13 C{ 1 H} NMR spectroscopy and mass spectrometry. The molecular structures of complexes 2, 3, and 5 were also determined by single-crystal X-ray diffraction analysis. © 2019 by the authors.

Fulltext

Inorganics

Synthesis of trithia-borinane complexes stabilized in diruthenium core: [(Cp*Ru) 2 (η 1 -S)(η 1 -CS){(CH 2 ) 2 S 3 BR}] (R = H or SMe)

In an effort to synthesize trithiocarbonate complexes of molybdenum and ruthenium, we carried out the reaction of CS2 with the intermediates, obtained from the reaction of [Cp#ML3X], (1: Cp# = C5Me5, M = Mo, L1 = L2 = L3 = CO, X = Me; 2: Cp# = C5H5, M = Ru, L1 = L2 = PPh3, X = Cl and 3: Cp# = C5H5, M = Fe, L1 = L2 = CO, X = I) and [LiBH4⋅thf]. The reactions led to formation of the trithiocarbonate complexes [Cp*Mo(CO)2(μ-ɳ2:ɳ1-CS3)(CO)3MoCp*] (4) [Cp*Mo(CO)2(ɳ2-S2CSMe)] (5) and [Cp*Mo(CO)2(ɳ2-S2CMe)] (6) in moderate yields. Treatment of [CpRu(PPh3)2Cl] (2) with [LiBH4⋅thf] followed by mild pyrolysis of CS2 yielded the trithiocarbonate ruthenium complex [CpRuPPh3(ɳ2-S2CSMe)] (7). All the new compounds have been characterized by various spectroscopic techniques and the structures of compounds 4, 5 and 7 were unequivocally established by crystallographic analysis. © 2017

Journal of Organometallic Chemistry

Synthesis and structural characterization of trithiocarbonate complexes of molybdenum and ruthenium derived from CS2 ligand

Reactions of the CS2 and CO2 heterocumulene ligands with nido-ruthenaborane cluster [1,2-(Cp∗Ru)2(μ-H)2B3H7], 1, were explored (Cp∗ = pentamethylcyclopentadienyl). Compound 1 when treated with CS2 underwent metal-assisted hydroboration to yield arachno-ruthenaborane [(Cp∗Ru)2(B3H8)(CS2H)], 2, with a dithioformato ligand attached to it. The chemistry of 2 was then explored with various transition metal carbonyl compounds under photolytic and thermolytic conditions. Thermolysis of 2 with [Mn2(CO)10] resulted in the formation of an unprecedented cubane-type cluster [(Cp∗Ru)2Mn(CO)3(CS2H2)B3H4], 3, with a rare [M3E5] formulation (E = B, S). On the other hand, when compound 2 was photolyzed in the presence of [Mn2(CO)10], it yielded an incomplete cubane-type cluster [(Cp∗Ru)2Mn(CO)3BH2(CS2H2)], 4. The room-temperature reaction of 2 with [Fe2(CO)9] yielded heterometallic arachno clusters [(Cp∗Ru)(CO)2{Fe(CO)3}2S2CH3], 6 and [(Cp∗Ru)2(B3H8)(CO){Fe(CO)3}2(CS2H)], 7. In contrast, photolysis of 2 with [Fe2(CO)9] yielded a tetrahedral cluster [(Cp∗Ru)(CO)2S(μ-H){Fe(CO)3}3], 8, tethered to an exo-polyhedral moiety [(Cp∗Ru)(CO)2]. Compound 6 provides an unusual bonding pattern by means of fusing the wing-tip vertex (S) of the [Fe2S2] butterfly core by an exo-polyhedral [(Cp∗Ru)(CO)2] unit. Density functional theory calculations were carried out to provide insight into the mechanistic pathway, electronic structure, and bonding properties. © 2014 American Chemical Society.

Inorganic Chemistry

Chemistry of diruthenium analogue of pentaborane(9) with heterocumulenes: Toward novel trimetallic cubane-type clusters

Synthesis of mono- and bi-metallic dithiocarboxylate-alkyne complexes from sunlight driven insertion reaction and their antibacterial activity

Organometallics

Organometallic Ionic Liquids from Cationic Arene–Ruthenium Complexes

Journal of Computational Chemistry

Multiwfn: A multifunctional wavefunction analyzer

The reaction of the [(η5-C5Me5) MoCl4] complex with [LiBH4·THF] in toluene at -70 °C, followed by pyrolysis at 110 °C, afforded dark brown [(η5-C5Me5Mo)3MoB 9H18], 2, in parallel with the known [(η5- C5Me5Mo)2B5H9], 1. Compound 2 has been characterized in solution by 1H, 11B, and 10C NMR spectroscopy and elemental analysis, and the structural types were unequivocally established by crystallographic studies. The title compound represents a novel class of vertex-fused clusters in which a Mo atom has been fused in a perpendicular fashion between two molybdaborane clusters. Electronic structure calculations employing density functional theory yield geometries in agreement with the structure determinations, and on grounds of density functional theory calculations, we have analyzed the bonding patterns in the structure . © 2010 American Chemical Society.

Journal	Data powered by TypesetEuropean Journal of Inorganic Chemistry
Publisher	Data powered by TypesetWiley-VCH Verlag
ISSN	14341948
Open Access	No