Oxidative Kupplung von Selenolat-Funktionen in (C6H5)3PC(Se)P(C6H5)3: Kristallstruktur von {[(C6H5)3P]2CSe} 22⊕Fe2OCl 26⊖ · 4 CH2Cl2 mit linearer FeOFe-Achse

The study of the nucleophilic degradation of S8 by the methanide complex [Mn(CO)4[(PPh2)2CH]] (2) has led to the preparation of a unique class of polysulfide derivatives of formula [(CO)4Mn[(PPh2)2C-Sn-C(PPh2)2]-Mn(CO)4]. The structures of 3 (n = 6), 4 (n = 2), and 7 (n = 1) have been determined by X-ray crystallography, whereas those polysulfides with the sulfur chains S7, S5, S4, and S3 have been detected by spectroscopic methods. The polysulfides with n > 2 lose sulfur spontaneously, a process that can be accelerated by treatment with PPh3 or Na/Hg. Complexes 3, 4, and 7 were protonated at the two methanide carbon atoms to give the cationic dinuclear derivatives [(CO)4Mn[(PPh2)2C(H)-Sn-C(H)-(PPh2)2]Mn(CO)4]2+ (8, n=6; 9, n=2; 10, n = 1). The 1H NMR spectrum of 9 suggests the existence of intramolecular C-H...S interactions, in agreement with the X-ray structural determination of this complex. By treatment of 4 and 7 with one equivalent of HBF4 it is possible to selectively protonate just one methanide carbon atom, which allows the isolation of the mixed cationic derivatives R(CO)4Mn[(PPh2)2C(H)-Sn-C(PPh2)2]Mn(CO)4]+ (11, n = 2; 6, n = 1). Additionally, heterometallic complexes containing a bridging disulfide unit, of general formula [(CO)4Mn[(PPh2)2C(AuPPh3)S-SC-(AuPPh3)(PPh2)2]Mn(CO)4]2+ (12) and [(CO)4Mn[(PPh2)2C(H)S-SC(AuPPh3)-(PPh2)2]Mn(CO)4]+ (13), were prepared by reaction of 4 and 11, respectively, with [AuCl(PPh3)] in the presence of TlPF6.

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Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

Ruiz

Ceroni

Quinzani

et al. 2001

Angew. Chem. Int. Ed.

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Oxidative Kupplung von Selenolat-Funktionen in (C6H5)3PC(Se)P(C6H5)3: Kristallstruktur von {[(C6H5)3P]2CSe} 22⊕Fe2OCl 26⊖ · 4 CH2Cl2 mit linearer FeOFe-Achse

Abstract: Das vollständige Manuskript dieser Zuschrift erscheint in: Angew. Chem. Suppl. 1983, 169. DOI:

Cited by 15 publications

References 5 publications

Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

New Approach to the Chemistry of Polysulfides Using Diphosphanylmethanide Complexes of Manganese(I)

Reversible S−S Bond Breaking and Bond Formation in Disulfide-Containing Dinuclear Complexes of MnI

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