Thiocarbonyl and related complexes of the transition metals

Yaneff, Philip V.

doi:10.1016/s0010-8545(00)80334-3

Cited by 157 publications

(43 citation statements)

References 97 publications

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“…94,95 However, in the case of gold these reactions have scarcely been studied and thus only two other CS 2 insertion reactions have been described so far, namely, those into the Au-C bond in [Au(η 1 -C 5 Me 5 )(PR 3 )] to give dithiocarboxylato complexes [Au(κ 1 -S 2 CC 5 Me 5 )(PR 3 ) n ] (R ) Ph, n ) 2; or R ) Pr i , n ) 1) 96 or into an Au-Cl bond of [Au 2 Cl 6 ] to give the chlorodithioformiato complex [AuCl 2 (κ 2 -S 2 CCl)]. 97 We have described the insertion of CS 2 into a Au-S (or S-H) bond in PPN[Au(SH) 2 ] to produce the first trithiocarbonato gold complex, [Au 2 (µ-κ 2 -CS 3 ) 2 ] 2-.…”

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confidence: 99%

Complexes with S-Donor Ligands. 7. New 1,1-Ethylenedithiolato Complexes of Thallium(I), Gold(I), and Gold(III): Syntheses, Structure, and Molecular Cubic Hyperpolarizabilities

Vicente¹,

Chicote²,

González‐Herrero³

et al. 1999

Inorg. Chem.

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beta-Diketonato complexes [Tl{CH{C(O)R}(2)}] or PPN[Au{CH{C(O)R}(2)}(2)] [where PPN = (Ph(3)P)(2)N] react with an excess of CS(2) to give, respectively, [Tl(2){S(2)C=C{C(O)R}(2)}](n)() [R = Me (1) or Ph (2)] or (PPN)(2)[Au(2){&mgr;-kappa(2)-S(2)C=C{C(O)R}(2)}(2)] [R = Me (3.PPN) or Ph (4.PPN)]. The gold complexes 3.PPN and 4.PPN can also be obtained from PPN[AuCl(2)] and the corresponding thallium 1,1-ethylenedithiolate. PPN[AuCl(4)] reacts with 1 to give PPN[Au{kappa(2)-S(2)C=C{C(O)Me}(2)}(2)] (5) which, in turn, reacts with PhICl(2), Br(2) or I(2) (1:1) to give PPN[AuX(2){kappa(2)-S(2)C=C{C(O)Me}(2)}] [X = Cl (6), Br (7), or I (8)]. By reacting 6 with TlCF(3)SO(3) and 1,10-phenanthroline (phen) in 1:2:1 molar ratio, the cationic complex [Au{kappa(2)-S(2)C=C{C(O)Me}(2)}(phen)]CF(3)SO(3) (9) can be obtained. The crystal structures of 5 and 6.0.5Me(2)CO have been determined. Third-order nonlinearities of 3.PPN, 3.Pr(4)N, 5, and 6 have been evaluated by the Z-scan technique; an increase in nonlinearity upon extending the pi-system is observed, with the anionic dimetallacycle containing two gold and four sulfur atoms in 3 responsible for the largest nonlinearities (approximately 100 x 10(-36) esu).

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confidence: 99%

Complexes with S-Donor Ligands. 7. New 1,1-Ethylenedithiolato Complexes of Thallium(I), Gold(I), and Gold(III): Syntheses, Structure, and Molecular Cubic Hyperpolarizabilities

Vicente¹,

Chicote²,

González‐Herrero³

et al. 1999

Inorg. Chem.

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“…Diese Reihe steht mit der an anderen Metallkomplexen gewonnenen Erfahrung in Einklang und bestätigt die anerkannte Rolle des Kohlenmonosulfid-Liganden als starker ji-Acceptor [13]. [25].…”

Section: Das Thiocarbonylosmium-systemunclassified

Metallkomplexe mit Tetrapyrrol-Liganden, XIX [1]. Synthese und elektrochemische Charakterisierung der Kohlenmonosulfid-Metalloctaethylporphyrine mit Eisen(II) oder Osmium(II) im Zentrum. Ein Beitrag zur "Bathochromie-Regel" / Metal Complexes with Tetrapyrrole Ligands, XIX [1]. Synthesis and Electrochemical Characterization of Thiocarbonyl Metallooctaethylporphyrins with Iron(II) or Osmium(II) in the Center. A Contribution to the "Rule of Bathochromism"

Buchler

Kokisch

Smith

et al. 1978

Zeitschrift Für Naturforschung B

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The preparation and spectroscopic characterization of thiocarbonyl metalloporphyrins M(OEP)CS(L') (e.g. 2e: M = Fe, L' = Py, 1e: M = Os, L' = Py** are described. Especially noteworthy is the existence of a pentacoordinate, diamagnetic, air-stable heme Fe(OEP)CS (2f: M = Fe, no L′). A linear correlation of the α-band frequencies (expressed as ϋa) in the optical spectrum and the metal(II/III) redox potentials (E1/2) taken from cyclic voltammetry experiments suggests (Abb. 3) that in complexes of the type M(OEP)LL' (1,2) λa is bathochromically shifted as the π-acceptor capacity of L increases (“Rule of Bathochromism”). The strong π-acceptor capacity of carbon monosulphide renders the attack of dioxygen to the thiocarbonyl heme unfavourable; O2 and CS seem to be comparable in their π-acceptor strength.

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“…1 Shortly thereafter, a number of other homoleptic metal carbonyls, including Fe(CO) 5 , Co 2 (CO) 8 , and Mo(CO) 6 , were synthesized using reactions of free metals with carbon monoxide at elevated pressures. The syntheses of additional homoleptic metal carbonyls of the first row transition metals such as V(CO) 6 , Cr(CO) 6 , and Mn 2 (CO) 10 required more sophisticated reductive carbonylation methods and occurred much later.…”

Section: Introductionmentioning

confidence: 99%

“…This certainly is the case with homoleptic metal thiocarbonyls such as Ni(CS) 4 . We report such computational studies designed to explore the structures and thermochemistry of both mononuclear homoleptic nickel thiocarbonyls Ni(CS) x (x = 4, 3, 2, 1) and binuclear homoleptic nickel thiocarbonyls Ni 2 (CS) x (x = 7, 6,5,4). The corresponding binuclear homoleptic nickel carbonyls Ni 2 (CO) x are not known experimentally in contrast to the stable well-known binuclear metal carbonyls Co 2 (CO) 8 , Fe 2 (CO) 9 , and Mn 2 (CO) 10 .…”

Section: Introductionmentioning

confidence: 99%

Cyclization of Thiocarbonyl Groups in Binuclear Homoleptic Nickel Thiocarbonyls To Give Ligands Derived from Sulfur Analogues of Croconic and Rhodizonic Acids

Gong

Luo

et al. 2014

Inorg. Chem.

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The sulfur analogue of the well-known Ni(CO)4, namely, Ni(CS)4, has been observed spectroscopically in low temperature matrices but is not known as a stable species under ambient conditions. Theoretical studies show that Ni(CS)4 with monomeric CS ligands and tetrahedrally coordinated nickel is disfavored by ∼17 kcal/mol relative to unusual isomeric Ni(C2S2)2 structures. In the latter structures the CS ligands couple pairwise through C-C bond formation to give dimeric S═C═C═S ligands, which bond preferentially to the nickel atom through their C═S bonds rather than their C═C bonds. Coupling of CS ligands in the lowest energy binuclear Ni2(CS)n (n = 7, 6, 5) structures results in cyclization to give remarkable CnSn (n = 5, 6) ligands containing five- and six-membered carbocyclic rings. Such ligands, which are the sulfur analogues of the well-known croconate (n = 5) and rhodizonate (n = 6) oxocarbon ligands, function as bidentate ligands to the central Ni2 unit. Higher energy Ni2(CS)n (n = 7, 6, 5) structures contain dimeric C2S2 ligands, which can bridge the central Ni2 unit. Dimeric C2S2 ligands rather than tetrathiosquare C4S4 ligands are found in the lowest energy Ni2(CS)4 structures.

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Thiocarbonyl and related complexes of the transition metals

Cited by 157 publications

References 97 publications

Complexes with S-Donor Ligands. 7. New 1,1-Ethylenedithiolato Complexes of Thallium(I), Gold(I), and Gold(III): Syntheses, Structure, and Molecular Cubic Hyperpolarizabilities

Complexes with S-Donor Ligands. 7. New 1,1-Ethylenedithiolato Complexes of Thallium(I), Gold(I), and Gold(III): Syntheses, Structure, and Molecular Cubic Hyperpolarizabilities

Cyclization of Thiocarbonyl Groups in Binuclear Homoleptic Nickel Thiocarbonyls To Give Ligands Derived from Sulfur Analogues of Croconic and Rhodizonic Acids

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