TY - JOUR
T1 - Dinuclear Gold(I) "A-Frame" Complexes from Geminal Diauration of 2,4-Diketones, Methylenedisulfones, and Cyanomethyl Sulfones
AU - Djordjevic, Bratislav
AU - Porter, Keith A.
AU - Nogai, Stefan
AU - Schier, Annette
AU - Schmidbaur, Hubert
PY - 2003/12/8
Y1 - 2003/12/8
N2 - Treatment of the disulfones RSO2CH2SO2R (R = Me, Ph) with 1 or 2 equiv of organolithium reagents, followed by metathesis with a (phosphine/arsine)gold(I) halide, afforded high yields of mono- or diaurated sulfones of the types [(R′3P)Au]CH(SO 2R)2 (R = R′ = Ph) and [(R′ 3P/As)Au]2{u-C(SO2R)2} (R = Me, R′3P = Ph3P, Ph2MeP, Ph3As; R = Ph, R′3P = PPh3, Ph2MeP). Using the same procedure, PhSO2CH2CN was transformed into [(Ph 3P)Au]2{u-C(CN)SO2Ph}. The products are stable to air and moisture and decompose at temperatures well above 150 °. The crystal structure analysis of the diaurated compounds reveals compact A-frame core units in which the central carbon atom forms a CAu2 triangle with an exceedingly small Au-C-Au angle and, consequently, a short aurophilic Au- - -Au contact. The corresponding angles S-C-S (or SAuC(N)) are widened in an overall distorted-tetrahedral environment. Attempted triauration using [(R′3P)Au]+BF4- reagents was unsuccessful with the disulfones but gave the adduct {[(Ph3P)Au] 2C(SO2Ph)CN[Au(PPh3)]}+BF 4-, in which the third gold atom is attached to the nitrile nitrogen atom. Benzyl phenyl sulfone was monoaurated to give the chiral product [(Ph3P)Au]CH(Ph)SO2Ph. 3-[(Triphenylphosphine)gold]pentane-2,4-dione was found to undergo a redistribution reaction induced by tritert-butoxyaluminum in benzene solution to give the diaurated diketone [(Ph3P)Au] 2{u-C{C(O)Me}2]. Its crystal structure shows a core unit with bonding characteristics similar to those of keto instead of sulfone/cyano substituents.
AB - Treatment of the disulfones RSO2CH2SO2R (R = Me, Ph) with 1 or 2 equiv of organolithium reagents, followed by metathesis with a (phosphine/arsine)gold(I) halide, afforded high yields of mono- or diaurated sulfones of the types [(R′3P)Au]CH(SO 2R)2 (R = R′ = Ph) and [(R′ 3P/As)Au]2{u-C(SO2R)2} (R = Me, R′3P = Ph3P, Ph2MeP, Ph3As; R = Ph, R′3P = PPh3, Ph2MeP). Using the same procedure, PhSO2CH2CN was transformed into [(Ph 3P)Au]2{u-C(CN)SO2Ph}. The products are stable to air and moisture and decompose at temperatures well above 150 °. The crystal structure analysis of the diaurated compounds reveals compact A-frame core units in which the central carbon atom forms a CAu2 triangle with an exceedingly small Au-C-Au angle and, consequently, a short aurophilic Au- - -Au contact. The corresponding angles S-C-S (or SAuC(N)) are widened in an overall distorted-tetrahedral environment. Attempted triauration using [(R′3P)Au]+BF4- reagents was unsuccessful with the disulfones but gave the adduct {[(Ph3P)Au] 2C(SO2Ph)CN[Au(PPh3)]}+BF 4-, in which the third gold atom is attached to the nitrile nitrogen atom. Benzyl phenyl sulfone was monoaurated to give the chiral product [(Ph3P)Au]CH(Ph)SO2Ph. 3-[(Triphenylphosphine)gold]pentane-2,4-dione was found to undergo a redistribution reaction induced by tritert-butoxyaluminum in benzene solution to give the diaurated diketone [(Ph3P)Au] 2{u-C{C(O)Me}2]. Its crystal structure shows a core unit with bonding characteristics similar to those of keto instead of sulfone/cyano substituents.
UR - http://www.scopus.com/inward/record.url?scp=0348252350&partnerID=8YFLogxK
U2 - 10.1021/om030585g
DO - 10.1021/om030585g
M3 - Article
AN - SCOPUS:0348252350
SN - 0276-7333
VL - 22
SP - 5336
EP - 5344
JO - Organometallics
JF - Organometallics
IS - 25
ER -