CARBONYL LIGANDS FROM ALKYNES - OXIDATIVE DECARBONATION OF ACETYLIDE BRIDGED COMPLEXES

被引：16

作者：

BERNHARDT, W ^{[1
]}

VAHRENKAMP, H ^{[1
]}

机构：

[1] UNIV FREIBURG,INST ANORGAN & ANALYT CHEM,ALBERTSTR 21,W-7800 FREIBURG,GERMANY

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 1990年 / 383卷 / 1-3期

关键词：

D O I：

10.1016/0022-328X(90)85142-L

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The organometal acetylides Cp(CO)2MCCR (1, M Fe, R Ph and 2, M Ru, R Ph, t-Bu, Me) react with Co2(CO)8 to form the acetylide bridged trinuclear complexes Co2(CO)6-μ-[Cp(CO)2MCCR] (3, M Fe, and 4, M Ru). Of these, the phenyl acetylide compounds undergo a non-destructive reaction with oxygen which results in the net loss of one carbon atom together with a CO ligand and the formation of the alkylidyne bridged clusters Co2MCp(CO)7(μ3-CPh) (5, M Fe, and 6, M Ru). The molecular structure of 6 has been determined by an X-ray analysis. The mechanism of the oxidation reaction has been elucidated by 13C labelling of the acetylide α-C atom and EI mass spectrometry. It has been found that this C atom is converted to CO which, with a probability of 7/9, ends up as a CO ligand in the product cluster. This means that the oxidation converts the α-C to CO before elimination of the CO ligands. © 1990.

引用

页码：357 / 366

页数：10

共 25 条

[1]

Abel E. W., 1970, Q REV CHEM SOC, V24, P498

[2] HETEROMETAL CLUSTERS FROM C-H CLEAVAGE OF CLUSTER-BOUND ACETYLENE LIGANDS [J].

BERNHARDT, W ;

VAHRENKAMP, H .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1988, 355 (1-3) :427-436

[3] OXIDATIVE DECARBONATION OF AN ACETYLIDE LIGAND [J].

BERNHARDT, W ;

VAHRENKAMP, H .

ORGANOMETALLICS, 1986, 5 (11) :2388-2389

[4]

BERNHARDT W, UNPUB

[5] MIXED METAL-CLUSTERS - METAL EXCHANGE VIA DINUCLEAR (CYCLOPENTADIENYL)METAL CARBONYLS [J].

BEURICH, H ;

BLUMHOFER, R ;

VAHRENKAMP, H .

CHEMISCHE BERICHTE-RECUEIL, 1982, 115 (07) :2409-2422

[6] MIXED METAL-CLUSTERS - METAL EXCHANGE VIA ORGANOMETAL DIMETHYLARSENIDES [J].

BEURICH, H ;

VAHRENKAMP, H .

CHEMISCHE BERICHTE-RECUEIL, 1982, 115 (07) :2385-2408

[7] MULTIPLE METAL EXCHANGE FOR MU-3-METHYLIDYNE TRICOBALT CLUSTERS [J].

BLUMHOFER, R ;

FISCHER, K ;

VAHRENKAMP, H .

CHEMISCHE BERICHTE-RECUEIL, 1986, 119 (01) :194-214

[8] NUCLEOPHILIC-ADDITION AT THE BRIDGING ETHYNYL LIGAND IN [OS3H(MU-3-C=CH)(CO)9] AND HYDROLYTIC CLEAVAGE OF THE CARBON CARBON TRIPLE BOND [J].

BOYAR, E ;

DEEMING, AJ ;

KABIR, SE .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (07) :577-579

[9] CYCLOPENTADIENYL-RUTHENIUM AND CYCLOPENTADIENYL-OSMIUM CHEMISTRY - SOME REACTIONS OF SUBSTITUTED VINYLIDENE COMPLEXES [J].

BRUCE, MI ;

SWINCER, AG ;

WALLIS, RC .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1979, 171 (01) :C5-C8

[10] SOME MORE TRANSITION-METAL ACETYLIDES [J].

BRUCE, MI ;

HUMPHREY, MG ;

MATISONS, JG ;

ROY, SK ;

SWINCER, AG .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1984, 37 (09) :1955-1961

← 1 2 3 →