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

Sundargopal Ghosh

Department Of Chemistry

Rongala Ramalakshmi

Chlorine compounds

Molybdenum

Reaction intermediates

reduction

ruthenium

Ruthenium compounds

Spectroscopic analysis

Synthesis (chemical)

CRYSTALLOGRAPHIC ANALYSIS

DITHIOACETATE

Ruthenium complexes

Spectroscopic technique

Structural characterization

Thiocarbonates

TRITHIOCARBONATE

Molybdenum compounds

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

Journal of Organometallic 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)

Reactivity of [Cp*Mo(CO)3Me], 1 with various chalcogenide ligands such as Li[BH2E3] and Li[BH3EFc] (E = S, Se or Te; Fc = (C5H5-Fe-C5H4)) has been described. Room temperature reaction of 1 with Li[BH2E3] (E = S and Se) yielded metal chalcogenide complexes [Cp*Mo(CO)2(η2-S2CCH3)], 2 and [Cp*Mo(CO)2(η1-SeC2H5)], 3. In compound 2, {Cp*Mo(CO)2} fragment adopts a four-legged piano-stool geometry with a η2-dithioacetate moiety. In contrast, treatment of 1 with Li[BH3(EFc)] (E = S, Se or Te; Fc = C5H5-Fe-C5H4) yielded borate complexes [Cp*Mo(CO)2(μ-H)(μ-EFc)BH2], 4-6 in moderate yields. Compounds 4-6 are too unstable and gradual conversion to [{Cp*Mo(CO)2}2(μ-H)(μ-EFc] (7: E = S; 8: Se) and [{Cp*Mo(CO)2}2(μ-TeFc)2], 9 happened by subsequent release of BH3. All the compounds have been characterized by mass spectrometry, IR, multinuclear NMR spectroscopy and structures were unequivocally established by crystallographic analysis for compounds 2, 3 and 7. © Indian Academy of Sciences.

Journal of Chemical Sciences

Reactivity of [Cp*Mo(CO)3Me] with chalcogenated borohydrides Li[BH2E3] and Li[BH3EFc] (Cp* = (η5-C5Me5); E = S, Se or Te; Fc = (C5H5-Fe-C5H4))

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

European Journal of Inorganic Chemistry

Reactivity of CS2– Syntheses and Structures of Transition-Metal Species with Dithioformate and Methanedithiolate Ligands

Building upon our earlier results on the chemistry of diruthenium analogue of pentaborane (9) with heterocumulenes, we continued to investigate the reactivity of arachno-[(Cp∗Ru)<inf>2</inf>(B<inf>3</inf>H<inf>8</inf>)(CS<inf>2</inf>H)], 1, (Cp∗ = η5-C<inf>5</inf>Me<inf>5</inf>) towards group 7 and 8 transition metal carbonyl compounds under photolytic and thermolytic conditions. The metal carbonyl compounds show diverse reactivity pattern with arachno-1. For example, the photolysis of arachno-1 with [Re<inf>2</inf>(CO)<inf>10</inf>] yielded [(Cp∗Ru)<inf>2</inf>B<inf>3</inf>H<inf>5</inf>(CH<inf>2</inf>S<inf>2</inf>){Re(CO)<inf>4</inf>}<inf>2</inf>], 2, [(Cp∗RuCO)<inf>2</inf>(μ-H)<inf>2</inf>(CH<inf>2</inf>S<inf>2</inf>){Re(CO)<inf>4</inf>}{Re(CO)<inf>3</inf>}], 3 and [(Cp∗Ru)<inf>2</inf>(μ-CO)(μ-H)(CH<inf>2</inf>S<inf>2</inf>){Re(CO)<inf>3</inf>}], 4. The geometry of 2 with a nearly planar eight-membered ring containing heavier transition metals rhenium, ruthenium is unprecedented. Compounds 3 and 4 can be considered as M<inf>4</inf>-quadrilateral and M<inf>3</inf>-triangle with a methylenedithiolato ligand attached to the metal centres, respectively. [Mn<inf>2</inf>(CO)<inf>10</inf>], on the other hand, reacts with arachno-1 to yield heterometallic binuclear [(Cp∗RuCO){Mn(CO)<inf>4</inf>}(μ-H)(SCH<inf>3</inf>)], 5 and homocubane [(Cp∗Ru)<inf>2</inf>{Mn(CO)<inf>3</inf>}-(CS<inf>2</inf>H<inf>2</inf>)B<inf>3</inf>H<inf>4</inf>], 6. In an attempt to generate group 8 analogues of 2-5, we performed the reaction of arachno-1 with [Fe<inf>2</inf>(CO)<inf>9</inf>] and [Ru<inf>3</inf>(CO)<inf>12</inf>]. Although, the objective of isolating analogous compounds was not achieved, the reaction with [Fe<inf>2</inf>(CO)<inf>9</inf>] led to novel tetrahedral cluster [(Cp∗RuCO){(Fe(CO)<inf>3</inf>}<inf>2</inf>S(μ-H)], 7. [Ru<inf>3</inf>(CO)<inf>12</inf>], in contrast, yielded known compounds [{Cp∗Ru(CO)}<inf>2</inf>B<inf>2</inf>H<inf>6</inf>], 9 and [Cp∗Ru(CO)<inf>2</inf>]<inf>2</inf>, 10. All the cluster compounds have been characterized by mass spectrometry, IR, and 1H, 11B, and 13C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis of 2-5 and 7. © The Royal Society of Chemistry.

Dalton Transactions

In search for new bonding modes of the methylenedithiolato ligand: novel tri- and tetra-metallic clusters

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

Room temperature photolysis of a triply-bridged borylene complex, [(μ3-BH)(Cp*RuCO)2(μ-CO)Fe(CO)3] (1 a; Cp*=C5Me5), in the presence of a series of alkynes, 1,2-diphenylethyne, 1-phenyl-1-propyne, and 2-butyne led to the isolation of unprecedented vinyl-borylene complexes (Z)-[(Cp*RuCO) 2(μ-CO)B(CR)(CHR′)] (2: R, R′=Ph; 3: R=Me, R′=Ph; 4: R, R′=Me). This reaction permits a hydroboration of alkyne through an anti-Markovnikov addition. In stark contrast, in the presence of phenylacetylene, a metallacarborane, closo-[1,2-(Cp*Ru) 2(μ-CO)2{Fe2(CO)5}-4-Ph-4,5- C2BH2] (5 a), is formed. A plausible mechanism has been proposed for the formation of vinyl-borylene complexes, which is supported by density functional theory (DFT) methods. Furthermore, the calculated 11B NMR chemical shifts accurately reflect the experimentally measured shifts. All the new compounds have been characterized in solution by mass spectrometry and IR, 1H, 11B, and 13C NMR spectroscopies and the structural types were unequivocally established by crystallographic analysis of 2, 5 a, and 5 b. Unique metal-borylene complexes: Photolysis of a triply bridged borylene complex [(μ3-BH) (Cp*RuCO)2(μ-CO)Fe(CO)3] (Cp*= η5-C5Me5) with various internal alkynes led to hydroboration yielding new vinyl-borylene complexes (see figure). A plausible mechanism has been proposed for the formation of vinyl-borylene complexes, which is supported by density functional theory (DFT) methods. Copyright © 2013 WILEY-VCH Verlag GmbH &amp; Co. KGaA, Weinheim.

Chemistry - A European Journal

Syntheses and characterization of new vinyl-borylene complexes by the hydroboration of alkynes with [(μ3-BH)(Cp*RuCO) 2(μ-CO)Fe(CO)3]

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

Journal	Data powered by TypesetJournal of Organometallic Chemistry
Publisher	Data powered by TypesetElsevier B.V.
ISSN	0022328X
Open Access	No