From chlorogermylenes to stable hydroxy- and siloxy-germylene-tungsten complexes

被引:48
作者
Bibal, C [1 ]
Mazières, S [1 ]
Gornitzka, H [1 ]
Couret, C [1 ]
机构
[1] Univ Toulouse 3, UMR 5069, Lab Heterochim Fondamentale & Appl, F-31062 Toulouse 04, France
关键词
D O I
10.1021/om020187y
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Reaction of the chlorogermylene ArGeCl [Ar = 2,6-bis((diethylamino)methyl)phenyl] with lithium amides afforded the aminogermylenes ArGeNR2 1 (1a, R = SiMe3; 1b, R = Pr-i); la was structurally analyzed by X-ray diffraction. A protic reagent such as 2,4,6-trimethylphenol (Ar'OH) reacts with 1b, leading to the mesityloxygermylene ArGeOAr' 2. Subsequent hydrolysis of tungsten complexes 1.W(CO)(5) gave ArGeOH-W(CO)(5),3. From la, ArGeOSiMe3.W(CO)(5) (4) also was obtained. Compounds 3 and 4 are the first stable hydroxy- and siloxygermylene complexes. X-ray analysis of 3 shows an increased coordination of the side-chain nitrogen atoms to the germanium resulting from the complexation Ge-->W. This complexation can also explain the significant acidity of the hydroxy group in 3, in the same range as triphenylgermanol Ph3GeOH.
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收藏
页码:2940 / 2943
页数:4
相关论文
共 30 条
[1]  
BANEY RH, 1959, CHEM IND-LONDON, P1129
[2]   Syntheses and crystal structures of heteroleptic stannylenes and germylenes [J].
Benet, S ;
Cardin, CJ ;
Cardin, DJ ;
Constantine, SP ;
Heath, P ;
Rashid, H ;
Teixeira, S ;
Thorpe, JH ;
Todd, AK .
ORGANOMETALLICS, 1999, 18 (03) :389-398
[3]  
Bibal C, 2001, ANGEW CHEM INT EDIT, V40, P952, DOI 10.1002/1521-3773(20010302)40:5<952::AID-ANIE952>3.0.CO
[4]  
2-S
[5]  
BIBAL C, UNPUB
[6]   BIVALENT GERMANIUM, TIN, AND LEAD 2,6-DI-TERT-BUTYLPHENOXIDES AND THE CRYSTAL AND MOLECULAR-STRUCTURES OF M(OC6H2ME-4-BUT2-2,6)2 (M=GE OR SN) [J].
CETINKAYA, B ;
GUMRUKCU, I ;
LAPPERT, MF ;
ATWOOD, JL ;
ROGERS, RD ;
ZAWOROTKO, MJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (06) :2088-2089
[7]   SUBVALENT GROUP-14 METAL-COMPOUNDS .14. THE X-RAY CRYSTAL-STRUCTURES OF 2 MONOMERIC GROUP-14 METAL BISAMIDES, GE[N(SIME3)2]2 AND SN[NC(ME)2(CH2)3CME2]2 [J].
CHORLEY, RW ;
HITCHCOCK, PB ;
LAPPERT, MF ;
LEUNG, WP ;
POWER, PP ;
OLMSTEAD, MM .
INORGANICA CHIMICA ACTA, 1992, 198 :203-209
[8]   Germanium-containing heterobicyclic 10-pi-electron ring systems. Synthesis and characterization of neutral and cationic germanium(II) derivatives of aminotroponiminates [J].
Dias, HVR ;
Wang, ZY .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (20) :4650-4655
[9]   Stable intramolecularly base-stabilized germylene- and stannylene-borane adducts:: M[C6H3(NMe2)2-2,6]2BH3 (M = Ge, Sn) [J].
Drost, C ;
Hitchcock, PB ;
Lappert, MF .
ORGANOMETALLICS, 1998, 17 (18) :3838-3840
[10]   The novel, chelating C,N-bidentate 2,6-bis(dimethylamino)phenyl ligand (R-), showing ambidentate N,N'-character in M(R)(2) (M=Ge, Sn, Pb) and Sn(R)X [X equals N(SiMe3)(2), CH(SiMe3)(2), Cl] [J].
Drost, C ;
Hitchcock, PB ;
Lappert, MF ;
Pierssens, LJM .
CHEMICAL COMMUNICATIONS, 1997, (12) :1141-1142