Experimental and theoretical studies of dinuclear gold(I) and gold(II) phosphorus ylide complexes. Oxidative addition, halide exchange, and structural properties including the crystal and molecular structures of [Au(CH2)2PPh2]2 and [Au(CH2)2PPh2]2(CH3)Br

Abstract

15in which the metal-metal separation more closely approaches that of the bis-(dipyrromethene) macrocycles at 5.145 (1) A, the copper(I1) ions are reduced to copper(1) via one dielectronic step.The variability of the nature of the two one-electron reductions of the dicopper(I1) sites suggests the utility of these complexes as catalysts for the activation of small molecules via concurrent two-electron reductions. Of considerable interest, in view of the simultaneous one-electron reduction steps in the CI-, N3-, and NCSsalts, is the potential of these complexes to catalyze the oxidation of organic substrates. Preliminary results in this direction indicate that the azido complex catalyzes the oxidation of 3,5di-tert-butylcatechol in the presence of molecular oxygen. These studies will be reported in detail elsewhere. (28) Agnus, Y . ; Remy, L.; Gisselbrecht, J.-P.; Weiss, R. J. Am. Chem. SOC. 1984, 106, 93-102.Acknowledgment. Support of this research by the University of Kansas Biomedical Sciences Support Grant 4306-071 1-9 is gratefully acknowledged. K.B.M. thanks Prof. Reynold T. Iwamoto for helpful discussions.Registry No. 1 ( n = 3), 98737-20-3; 3,3'-diethyl-5,5'-diformyl-4,4'dimethyldipyrromethane, 967-68-0; 1,3-propanediamine, 109-76-2; Pb2-(bi-dptmd)(SCN),, 98759-99-0; Zn,(bi-dptmd)(CI),, 98760-00-0; Cu2-(bi-dptmd)(CI),, 98760-01-1; Cu2(bi-dptmd)(CIO4),, 98760-02-2; Cu,-(bi-dptmd)(BF,),, 9308 1-48-2; C~2(bi-dptmd)(N~)~.'/~CH,OH, 98760-04-4; Cu2(bi-dptmd)(SCN),, 98760-05-5; Zn2(bi-dpen)(C1),, 98760-06-6; C~~(bi-dpen)(ClO,)~, 98777-04-9; C~~(bi-dptmd)(N,)~, 98760-03-3; ethylenediamine, 107-1 5-3.

The structure of [Au-μ-{3,5-(C6H5)2C3HN2}]3Cl2: a trinuclear mixed-valence gold pyrazolate complex

“…Our studies of dinuclear and trinuclear late transition metal complexes (Basil et al, 1985;Murray, Briggs, Garz6n, Raptis, Porter & Fackler, 1987) have led to the characterization of complexes containing gold in the I, II, III as well as mixed I/III oxidation states. The structural features of complexes containing gold in more than one oxidation state are of particular interest.…”

The structure of tetrachlorobis-μ-[dimethylenediphenylphosphato(V)-C,C']-digold(III) dihydrate, [Au(CH2)2P(C6H5)2]2Cl4.2H2O,an organometallic dinuclear gold(III) ylide complex containing chloride ligands

“…The eis, trans isomer of the title complex has been previously reported (Dudis & Fackler, 1985). In that structure, Au-C1 bond distances at the trans gold center measure 2.295 (9) and 2.272 (9)/~,, compared with 2.338 (9) and 2.360 (7)A at the eis gold center.…”

“…In a limited number of instances, isomerization reactions have been observed (Dudis & Fackler, 1985), as well as cleavage reactions leading to mononuclear gold(I) products (Porter, Knachel & Fackler, 1986).…”

Die Suche nach einkernigem Gold(II) und seine mögliche Rolle in Photokatalyse und Medizinalchemie

“…[9] Alternativ zur Disproportionierung wird Gold(II) durch Dimerisierung unter Bildung einer Au 2 4+ -Einheit oder durch Oligomerisierung zu Clusterverbindungen stabilisiert. [5,[10][11][12] Yamund Mitarbeiter berichteten über eine unverbrückte Au-Au-Bindung (Au-Au2 .6117 )i mK omplex [(dppn)ClAu II -Au II Cl(dppn)] 2+ (dppn = 1,8-Bis(diphenyl-phosphanyl)naphthalin, Schema 1). [5] Dieser Pfad wird besonders durch die Au-Au-Bindung potentiell verbrückende Liganden, wie SO 4 2À (Au-Au2 .490 ), [CH 2 PR 2 CH 2 ] À oder [S 2 CNR 2 ] À (2.550-2.694 ), bevorzugt.…”

“…[5] Dieser Pfad wird besonders durch die Au-Au-Bindung potentiell verbrückende Liganden, wie SO 4 2À (Au-Au2 .490 ), [CH 2 PR 2 CH 2 ] À oder [S 2 CNR 2 ] À (2.550-2.694 ), bevorzugt. [5,[10][11][12] Yamund Mitarbeiter berichteten über eine unverbrückte Au-Au-Bindung (Au-Au2 .6117 )i mK omplex [(dppn)ClAu II -Au II Cl(dppn)] 2+ (dppn = 1,8-Bis(diphenyl-phosphanyl)naphthalin, Schema 1). [13] Kürzlich verwirklichten Bochmann et al im Komplex (C^N^C)Au II -Au II -(C^N^C) mit einem doppelt cyclometallierten 2,6-Bis(4'-tertbutylphenyl)pyridin-Liganden eine weitere unverbrückte, kurze Au-Au-Bindung (Au-Au2 .4941 )( Schema 1).…”