Electron-rich siloxane-platinum complexes - Synthesis, structures, and reactivity

被引：10
作者：
Goikhman, R
Karakuz, T
Shimon, LJW
Leitus, G
Milstein, D [1 ]
机构：
[1] Weizmann Inst Sci, Dept Organ Chem, IL-76100 Rehovot, Israel
[2] Weizmann Inst Sci, Unti Chem Res Support, IL-76100 Rehovot, Israel
来源：
CANADIAN JOURNAL OF CHEMISTRY | 2005年 / 83卷 / 6-7期
关键词：
cyclosiloxane; metallacycle; platinum silyl; Lewis base; oxidative addition;
D O I：
10.1139/V05-041
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
New platinasiloxanes were synthesized and their reactivity was studied. Oxidative addition of ( HSiMe2) O-2 to Pt( PEt3)(3) led to dehydrogenation and quantitative formation of the four- membered platinacyclosiloxane [( PEt3)(2)Pt(( SiMe2) O-2)] which was characterized by X- ray diffraction. This complex was stable towards non- polar substrates and aerobic conditions, but reacted readily with electrophiles and Lewis acids. Reaction with MeI resulted in ring opening, while MeOTf gave an oxonium complex, with retention of the platinacycle structure. A complex resulting from BF3 coordination to the ring oxygen atom was also obtained. An unprecedented open- chain diplatinasiloxane containing the Pt - Si - O - Si - O - Si - Pt fragment was formed by oxidative addition of H - SiMe2 - O - SiMe2 - O - SiMe2 - H to Pt( PEt3) (3) and it was characterized by X- ray diffraction.
引用
收藏
页码：786 / 792
页数：7
相关论文
共 24 条
[1]   SMALL RING METALLACYCLES .6. METAL-CATALYZED REDISTRIBUTIONS OF ORGANOSILANES .5. PREPARATION OF CYCLOMETALLADISILOXANES OF THE TYPE M(SIMEROSIMER) (R = PHENYL AND BENZYL) AND THE CATALYZED REDISTRIBUTION OF (HRMESI)2O [J].
BELL, LG ;
GUSTAVSON, WA ;
THANEDAR, S ;
CURTIS, MD .
ORGANOMETALLICS, 1983, 2 (06) :740-745
[2]   First platinum clusters containing a direct Pt-Si bond:: molecular structure of [Pt3{Si(OSiMe3)3} (μ-PPh2)3(PPh3)2] and electrochemical studies [J].
Bender, R ;
Braunstein, P ;
Bouaoud, SE ;
Merabet, N ;
Rouag, D ;
Zanello, P ;
Fontani, M .
NEW JOURNAL OF CHEMISTRY, 1999, 23 (11) :1045-1047
[3]   (ETA-5-CYCLOPENTADIENYL)TRIALKYLPLATINUM PHOTOHYDROSILYLATION CATALYSTS - MECHANISM OF ACTIVE CATALYST FORMATION AND PREPARATION OF A NOVEL BIS(SILYL)PLATINUM HYDRIDE [J].
BOARDMAN, LD .
ORGANOMETALLICS, 1992, 11 (12) :4194-4201
[4]   SMALL RING METALLOCYCLES .4. SYNTHESIS AND CHEMICAL REACTIVITY OF CYCLO-METALLADISILOXANES, MSIR2OSIR2, AND CYCLO-METALLADISILABUTANES, MSIR2CH2SIR2 [J].
CURTIS, MD ;
GREENE, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1978, 100 (20) :6362-6367
[5]   Hydrosilylation of vinylsiloxanes with hydrosiloxanes in the presence of thermo- and photoactivated platinum(II) phosphine complexes [J].
de Vekki, DA ;
Skvortsov, NK .
RUSSIAN JOURNAL OF GENERAL CHEMISTRY, 2004, 74 (02) :197-206
[6]  
DRAKE R, 1998, CHEM ORGANIC SILICON, P2217
[7]   PREPARATION OF SILYLPLATINUM COMPLEXES BY INTERACTION OF ORGANOSILICON HYDRIDES AND "CARBONATOBIS(PHOSPHINE)PLATINUM(II) COMPLEXES [J].
EABORN, C ;
METHAM, TN ;
PIDCOCK, A .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1975, (21) :2212-2214
[8]   SOME PLATINUM COMPLEXES CONTAINING CHELATING BIS(SILYL) LIGANDS [J].
EABORN, C ;
METHAM, TN ;
PIDCOCK, A .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1973, 63 (DEC16) :107-117
[9]   THE REACTION OF METHYLDISILOXANES AND 1-1-DIMETHYLDISTILTHIANE WITH BORON AND HYDROGEN HALIDES [J].
EMELEUS, HJ ;
ONYSZCHUK, M .
JOURNAL OF THE CHEMICAL SOCIETY, 1958, (FEB) :604-609
[10]   Iridium- and rhodium-silanol complexes: Synthesis and reactivity [J].
Goikhman, R ;
Aizenberg, M ;
Shimon, LJW ;
Milstein, D .
ORGANOMETALLICS, 2003, 22 (20) :4020-4024
123