Investigation into the reactivity of the metal-metal triple bond in [Cp'(CO)2M]2 (Cp' = .eta.5-C5Me5', M = Mo, W) vs. elemental sulfur. Formation of different Cp'2M2S4 isomers and crystal structures of Cp'2Mo2(.mu.-S2)(.mu.-S)2 and Cp'2(CO)2W2(.mu.-S)2S

Brunner, Henri; Meier, W.; Wächter, Joachim; Guggolz, Ernst; Zahn, Thomas; Ziegler, Manfred L.

doi:10.1021/om00069a001

Cited by 91 publications

(47 citation statements)

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“…The other systems in Figure 3, [Cp'Re(m-S 2 ) 2 ReCp'] 2+ (7, Cp' = h 5 -C 5 EtMe 4 ) [10] and [Cp*Mo(m-S 2 )(m-S) 2 MoCp*] (8) [11] contain two electrons less than 5. In 7, two sides of the S 4 rectangle are clearly nonbonding (3.24 ), while the Re À Re separation is as short as 2.60 .…”

supporting

confidence: 71%

“…The other systems in Figure 3, [Cp'Re(m-S 2 ) 2 ReCp'] 2+ (7, Cp' = h 5 -C 5 EtMe 4 ) [10] and [Cp*Mo(m-S 2 )(m-S) 2 MoCp*] (8) [11] contain two electrons less than 5. 1 ).…”

Section: àmentioning

confidence: 99%

“…In the experimental geometry (right side), b 2 is populated in place of 2a 1 (d 1 ), which becomes the new lowest unoccupied molecular orbital (LUMO). Given the d d -p p antibonding character of the latter, the proposed MoÀMo double bond in 8 [11] (2.599 ) seems questionable, and multiple MÀS bonding character can be instead assumed.…”

mentioning

confidence: 99%

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S₄²⁻ Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

et al. 2008

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A sulfur atom, with its six valence electrons, may reach an octet by association into S n rings. Two-electron reduction of the rings usually leads to polysulfide chains S n 2À . Small, neutral S n rings are rare; witness S 4 , for which there is scant evidence [1] and continuing theoretical uncertainty about its structure.[2] As is the case for S 3 , the S 4 rings instability is presumably due to lone-pair repulsion. On the other hand, coordinated S 4 2À most certainly exists, and as we will see, not only as a simple chain (of which Na 2 S 4 is an example [3] ). This paper moves toward an understanding of the variety of complexed S 4 2À structural types and in the process shows that some compounds which hitherto have been considered as disulfide complexes may be profitably seen as containing D 2h -distorted S 4 2À rings. Their formation is attributable to a coupling redox process induced by either an external oxidant or inner oxidation of coordinated metal centers. The analysis leads us to the problem of tuning the S 2 2À /2 S 2À interconversion as well. The electronic structure of some compounds in the literature is reinterpreted, and, we believe, there emerges the outline of a consistent way of thinking about redox coupling of sulfides and disulfides. . [4] In these chair-like complexes, the S 4 rectangle has rather different S···S sides (e.g., 2.049(3) vs. 2.894(3) in 1), the shorter ones being either along (in 1) or across (in 2) the MÀM bonds. Compound 1 is obtained upon 2-e À oxidation of the binuclear precursor [Cp*Ir(m-CH 2 ) 2 (m-S 2 )IrCp*] (3), [4] in which the d 7 metal centers reach saturation with a formal Ir À Ir bond (whose actual length is 2.642(1) ). The local geometry of the binuclear metal components is virtually unchanged in 1. Our theoretical analysis [5] shows that the most dramatic effect of coupling (if there were no oxidation) is the destabilization of the s* combinations formed, in the S 4 plane, by the p k * and p k S 2 populated levels (s 2 * and s 1 * in Figure 2 a, b). These are already in antibonding relationships (therefore destabilized) with the populated d*-d* and d-d metal combinations: s 2

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supporting

confidence: 71%

“…The other systems in Figure 3, [Cp'Re(m-S 2 ) 2 ReCp'] 2+ (7, Cp' = h 5 -C 5 EtMe 4 ) [10] and [Cp*Mo(m-S 2 )(m-S) 2 MoCp*] (8) [11] contain two electrons less than 5. 1 ).…”

Section: àmentioning

confidence: 99%

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S₄²⁻ Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

et al. 2008

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“…Reaction of [W 2 (CO) 4 Cp* 2 ] with sulfur gives the unsymmetrical complex [W 2 (u-S) 2 (S)(CO) 2 Cp* 2 ] (34), which on further reaction produces two isomers of [W 2 S 4 Cp* 2 ], analogous to (31a) and (31c) above. 991 ' 1073 Like its molybdenum analogue, [W 2 (S) 2 (n-S) 2 Cp 2 ] reacts with acetylene to give the ji-dithiolene complex [W 2 (u-SCH=CHS) 2 Cp 2 ] but the chelating dithiolene complexes [W 2 (S)(u-S) 2 (SCH=CHS)Cp 2 ] and [W 2 (u-S) 2 (SCH=CHS) 2 Cp 2 ] are also formed; the analogous SCH 2 CH 2 S species are available from the reaction of [WH(CO) 3 Cp] with ethylene sulfide. 1074 The reaction of [WH(CO) 3 Cp] with S(NMe 2 ) 2 produces [{W(CO) 3 Cp} 2 (u-S)], which reacts with CH 2 N 2 to give the thioformaldehyde complex [W 2 (CO) 4 (u-SCH 2 )Cp 2 ].…”

Section: Tungsten Complexes With Sulfur And/or Thiolate Ligandsmentioning

confidence: 99%

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Morris

1995

Comprehensive Organometallic Chemistry II

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“…Eine Reihe von Cp*W-Sulfido-Komplexen wurde bei Umsetzungen von 1 mit H 2 S [11] oder mit Lithiumorganosulfid-Reagenzien (wie LiS t Bu [8,12,14]) erhalten; in anderen Fa Èllen wurde Cp*W(O) 2 R (R = Me, CH 2 SiMe 3 ) in Gegenwart von B 2 S 3 umgesetzt [3,9] oder Schwefel an die WºW Dreifachbindung von [Cp*W(CO) 2 ] 2 addiert [13,20].…”

Section: Introductionunclassified

Chalkogen-Derivate der Halbsandwich-Wolfram(V)-Komplexe CpWCl4 und CpWCl4(PMe3). Röntgen-Kristallstrukturanalysen vonanti-[CpW(Se)(μ-Se)]2 und CpW(S)2(OMe)

Herberhold¹,

Jin²,

Milius³

2001

Z. anorg. allg. Chem.

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Bei der Chalkogenierung von Cp*WCl4 (1) mit E(SiMe3)2 (E = S, Se) und Te(SiMe2tBu)2 in Chloroform‐Lösung entstehen zweikernige Produkte des Typs anti‐[Cp*W(E)(μ‐E)]2 (E = S (3 a), Se (3 b) und Te (3 c)). Für 3 b wurde eine Röntgenstrukturanalyse durchgeführt; das zentrosymmetrische Molekül enthält einen planaren W(μ‐Se)2W‐Ring, der W–W‐Abstand (297.9(1) pm) entspricht einer Einfachbindung. In Gegenwart von Luftsauerstoff werden die beiden terminalen Chalkogenido‐Liganden (E) in 3 a–c schrittweise durch Oxido‐Liganden (O) ersetzt, wobei sich quantitativ [Cp*W(O)(μ‐E)]2 (E = S (5 a), Se (5 b) bzw. Te (5 c)) bildet. Die Umsetzung von Cp*WCl4 (1) mit H2S oder (NH4)2Sx (x ∼ 10) führt zu Cp*W(S)2Cl (6 a); das entsprechende Methoxy‐Derivat Cp*W(S)2OCH3 (9 a) wurde strukturanalytisch charakterisiert. Dagegen ergibt Cp*WCl4(PMe3) (2) mit Dinatrium‐Tetrasulfid, Na2S4, in DimethylformamidLösung ein Gemisch aus einkernigem Cp*W(S)(S2)Cl (8 a), zweikernigem [Cp*W(S)(μ‐S)]2 (3 a) und einem dreikernigen Nebenprodukt der Zusammensetzung Cp*2W3S7 (13 a). Endständige Sulfido‐Liganden werden in Lösung in Gegenwart von Sauerstoff gegen endständige Oxido‐Liganden ausgetauscht; so geht 6 a stufenweise in Cp*W(O)(S)Cl (10 a) bzw. CpW(O)2Cl (12 a) über, während 8 a in Cp*W(O)(S2)Cl (11 a) und 13 a in Cp*2W3(O)S6 (14 a) umgewandelt werden. Die Disulfido‐Komplexe 8 a und 11 a lassen sich mit Triphenylphosphan unter Bildung von 6 a bzw. 10 a desulfurieren. Die neuen Komplexe wurden anhand ihrer IR‐ und NMR‐Spektren sowie durch Massenspektrometrie charakterisiert.

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Investigation into the reactivity of the metal-metal triple bond in [Cp'(CO)2M]2 (Cp' = .eta.5-C5Me5', M = Mo, W) vs. elemental sulfur. Formation of different Cp'2M2S4 isomers and crystal structures of Cp'2Mo2(.mu.-S2)(.mu.-S)2 and Cp'2(CO)2W2(.mu.-S)2S

Cited by 91 publications

References 0 publications

S₄²⁻ Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

S₄²⁻ Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Chalkogen-Derivate der Halbsandwich-Wolfram(V)-Komplexe CpWCl4 und CpWCl4(PMe3). Röntgen-Kristallstrukturanalysen vonanti-[CpW(Se)(μ-Se)]2 und CpW(S)2(OMe)

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Investigation into the reactivity of the metal-metal triple bond in [Cp'(CO)2M]2 (Cp' = .eta.5-C5Me5', M = Mo, W) vs. elemental sulfur. Formation of different Cp'2M2S4 isomers and crystal structures of Cp'2Mo2(.mu.-S2)(.mu.-S)2 and Cp'2(CO)2W2(.mu.-S)2S

Cited by 91 publications

References 0 publications

S42− Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

S42− Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

Cyclopentadienyl Complexes of Chromium, Molybdenum and Tungsten

Chalkogen-Derivate der Halbsandwich-Wolfram(V)-Komplexe Cp*WCl4 und Cp*WCl4(PMe3). Röntgen-Kristallstrukturanalysen vonanti-[Cp*W(Se)(μ-Se)]2 und Cp*W(S)2(OMe)

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S₄²⁻ Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

S₄²⁻ Rings, Disulfides, and Sulfides in Transition‐Metal Complexes: The Subtle Interplay of Oxidation and Structure

Chalkogen-Derivate der Halbsandwich-Wolfram(V)-Komplexe CpWCl4 und CpWCl4(PMe3). Röntgen-Kristallstrukturanalysen vonanti-[CpW(Se)(μ-Se)]2 und CpW(S)2(OMe)