CS2, CSSe und CSe2 als Bausteine für ein- und zweikernige Palladium- und Platinkomplexe [1] / CS2, CSSe and CSe2 as Building Blocks for Mono- and Binuclear Palladium and Platinum Complexes [1]

Werner, Helmut; Ebner, Martin; Bertleff, W.

doi:10.1515/znb-1985-1020

Cited by 26 publications

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References 20 publications

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“…Carbon disulfide coordinates to a transition metal in a variety of modes: both mononuclear complexes, where CS 2 binds the metal either η 1 -end-on or η 2 -side-on, and polynuclear derivatives have been reported . Numerous types of coordination have been observed in these cases, with the CS 2 molecule unsymmetrically bridging di- or trimetallic moieties (Chart 1).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Pd₄(μ-P^tBu₂)₂(μ-CS₂)(PPh₃)₂I₂, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS₂ Molecule Bridging Four Palladium Centers

et al. 1997

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The dinuclear CS2 complex [Pd2(μ-PtBu2)(μ,η2:η2-CS2)(PPh3)2]BF4, (2)BF4, reacts with Me4NI to yield the neutral tetranuclear Pd(I) derivative Pd4(μ-PtBu2)2(μ4-CS2)(PPh3)2I2 (4), which has been characterized by single-crystal X-ray diffraction. Its unusual molecular structure with a formally hexacoordinate carbon atom, as well as that of (2)+ with a planar tetracoordinate carbon can be explained on the basis of fragment MO considerations and EHMO model calculations. The reaction proceeds stepwise, with the relatively fast substitution of CS2 by the iodide ion giving the intermediate complex Pd2(μ-PtBu2)(μ-I)(PPh3)2 (3). The latter further reacts slowly with free CS2 to give complex 4 and free PPh3. Complex 3 was also prepared and isolated pure by reacting [Pd2(μ-PtBu2)(PPh3)3]BF4 with Me4NI.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Structure of Pd₄(μ-P^tBu₂)₂(μ-CS₂)(PPh₃)₂I₂, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS₂ Molecule Bridging Four Palladium Centers

et al. 1997

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Komplexe mit Kohlenstoffsulfiden und ‐seleniden als Liganden, XVIII. Umwandlung η²‐gebundener Heteroallene (CS₂, CSSe und CSe₂) in CS‐, CSSe und C₂Se‐Chelatliganden

Ebner

Werner

1986

Chem. Ber.

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PPh3)2Pt(q2-CS2) (1) reagiert rnit PMe3, PMe2Ph und PMePh2 zu den (Trithiocarbonato-S,S')platin(II)-Komplexen (PR3)2Pt(q2-S2CS) (2-4). Analog entsteht bei der Umsetzung von (PPh,),Pt(q2-CSSe) mit PMe3 die Verbindung (PMe3)2Pt(q2-Se2CS) (6). Die Reaktion von (PPh,)2Pt(q2-CSe2)d(7) rnit PMe2Ph fiihrt zu dem Metallaheterocyclus (PMe2Ph)-(PPh3)PtSeC(Se)Se (Se) (8). Bei der Einwirkung von C 0 2 auf (PPhs)2Pt(C2H4) bildet sich der Carbonatoplatin(T1)-Komplex (PPh3)2Pt(q2-02CO) (9). Ein Vorschlag zum Bildungsmechanismus der erhaltenen Produkte wird diskutiert. Metal Complexes with Carbon Sulfides and Selenides as Ligands, XVIII') Conversion of q'-Bonded Heteroallenes (CS, C S , and CSeJ into the Chelate LigandsCg-, CSSei-, and C2Sei-(PPh3kPt(q2-C&) (1) reacts with PMe3, PMe,Ph, and PMePh2 to produce the (trithiocarbonato-S,S')platinum(II) complexes (PR3),Pt(q2-S2CS) (2 -4). Similarly, on treatment of (PPh,kPt(q2-CSSe) with PMe, the compound (PMe&Pt(q2-Se2CS) (6) is formed. The re-(7) with PMe2Ph leads to the metallaheterocycle (PMe2Ph)carbonatoplatinum(I1) complex (PPh3)2Pt(qz-OzCO) (9) is obtained from (PPh,)2Pt(C2H4) and COz. The mechanism of formation of the chelate compounds is discussed.

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Complexes with carbon sulfides and selenides as ligands, XXIII. Synthesis of Pt(CS)(PPh ₃ ) ₂ ) and Pt(CE)(dpmb) (E = S, Se): The First Mononuclear Thio‐ and Selenocarbonyl Complexes of Platinum(0)

Ebner

Werner

1988

Chem. Ber.

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PPh&Pt(p-CS2)Pt(PPh3k (1) and (dpmb)Pt(p-C&)Pt(PPh3)2 (2: E = S; 3 E = Se) an heating at 40-70°C give the complexes Pt(CS)(PPb,k (4) and Pt(CEXdpmb) (S: E = S; 6 E = Se), which are the first mononuclear thio-and selenocarbonyl complexa of platinum(0).The most common method of generating a CS or CSe ligand in the coordination sphere of a transition metal, namely the abstraction of a sulfur or selenium atom from coordinated CS2 or CSe2 by ph~sphanes~,~', has failed thus far with Pd(0) and Pt(0). Treatment of the complexes M(q2-CS2)(PPhJ2 and M(q2-CSe2)(PPh3)2 (M = Pd, Pt) with PMe3, PMe2Ph, PMePh2 etc. does not lead to the formation of the corresponding thio-and selenocarbonyl compounds M(CE)(PPh3)2 (E = S, Se), but to mono-or dinuclear products containing P R~C S T ,

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CS₂, CSSe und CSe₂ als Bausteine für ein- und zweikernige Palladium- und Platinkomplexe [1] / CS₂, CSSe and CSe₂ as Building Blocks for Mono- and Binuclear Palladium and Platinum Complexes [1]

Abstract: The compounds Pd(PPh3)4, Pt(PPh3)4 and Pt(PPr3i)2 react with CS2, CSSe and CSe2 to give the mononuclear complexes (PR3)2M(η2-CEE′). From Pd(PPh3)4 and excess CSe2 the compound (PPh3<… Show more

Cited by 26 publications

References 20 publications

Synthesis and Structure of Pd₄(μ-P^tBu₂)₂(μ-CS₂)(PPh₃)₂I₂, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS₂ Molecule Bridging Four Palladium Centers

Synthesis and Structure of Pd₄(μ-P^tBu₂)₂(μ-CS₂)(PPh₃)₂I₂, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS₂ Molecule Bridging Four Palladium Centers

Komplexe mit Kohlenstoffsulfiden und ‐seleniden als Liganden, XVIII. Umwandlung η²‐gebundener Heteroallene (CS₂, CSSe und CSe₂) in CS‐, CSSe und C₂Se‐Chelatliganden

Complexes with carbon sulfides and selenides as ligands, XXIII. Synthesis of Pt(CS)(PPh ₃ ) ₂ ) and Pt(CE)(dpmb) (E = S, Se): The First Mononuclear Thio‐ and Selenocarbonyl Complexes of Platinum(0)

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CS2, CSSe und CSe2 als Bausteine für ein- und zweikernige Palladium- und Platinkomplexe [1] / CS2, CSSe and CSe2 as Building Blocks for Mono- and Binuclear Palladium and Platinum Complexes [1]

Abstract: The compounds Pd(PPh3)4, Pt(PPh3)4 and Pt(PPr3i)2 react with CS2, CSSe and CSe2 to give the mononuclear complexes (PR3)2M(η2-CEE′). From Pd(PPh3)4 and excess CSe2 the compound (PPh3<… Show more

Cited by 26 publications

References 20 publications

Synthesis and Structure of Pd4(μ-PtBu2)2(μ-CS2)(PPh3)2I2, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS2 Molecule Bridging Four Palladium Centers

Synthesis and Structure of Pd4(μ-PtBu2)2(μ-CS2)(PPh3)2I2, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS2 Molecule Bridging Four Palladium Centers

Komplexe mit Kohlenstoffsulfiden und ‐seleniden als Liganden, XVIII. Umwandlung η2‐gebundener Heteroallene (CS2, CSSe und CSe2) in CS‐, CSSe und C2Se‐Chelatliganden

Complexes with carbon sulfides and selenides as ligands, XXIII. Synthesis of Pt(CS)(PPh 3 ) 2 ) and Pt(CE)(dpmb) (E = S, Se): The First Mononuclear Thio‐ and Selenocarbonyl Complexes of Platinum(0)

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CS₂, CSSe und CSe₂ als Bausteine für ein- und zweikernige Palladium- und Platinkomplexe [1] / CS₂, CSSe and CSe₂ as Building Blocks for Mono- and Binuclear Palladium and Platinum Complexes [1]

Synthesis and Structure of Pd₄(μ-P^tBu₂)₂(μ-CS₂)(PPh₃)₂I₂, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS₂ Molecule Bridging Four Palladium Centers

Synthesis and Structure of Pd₄(μ-P^tBu₂)₂(μ-CS₂)(PPh₃)₂I₂, a Neutral Palladium(I) Derivative with a Hexacoordinate Carbon and a CS₂ Molecule Bridging Four Palladium Centers

Komplexe mit Kohlenstoffsulfiden und ‐seleniden als Liganden, XVIII. Umwandlung η²‐gebundener Heteroallene (CS₂, CSSe und CSe₂) in CS‐, CSSe und C₂Se‐Chelatliganden

Complexes with carbon sulfides and selenides as ligands, XXIII. Synthesis of Pt(CS)(PPh ₃ ) ₂ ) and Pt(CE)(dpmb) (E = S, Se): The First Mononuclear Thio‐ and Selenocarbonyl Complexes of Platinum(0)