Electrophilic addition to η2-aldehyde complexes of pentaamineosmium(II):: The formation of Fischer carbyne complexes via η2-aldehydium intermediates

被引:17
作者
Spera, ML [1 ]
Chen, HY [1 ]
Moody, MW [1 ]
Hill, MM [1 ]
Harman, WD [1 ]
机构
[1] Univ Virginia, Dept Chem, Charlottesville, VA 22901 USA
关键词
D O I
10.1021/ja972766d
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A series of eta(2)-aldehyde complexes of pentaammineosmium(II) of the form [Os(NH3)(5)(L)](OTf)(2) (L = formaldehyde (1), acetaldehyde (2), trimethylacetaldehyde (3), benzaldehyde (4), and crotonaldehyde (5), OTf = trifluoromethanesulfonate) are prepared and characterized. Treatment of these eta(2)-bound aldehyde complexes with CH3OTf affords Fischer carbyne complexes 14-18 with typical yields ranging from 25-92%. Protonation (HOTf/MeCN) or methylation (MeOTf/DME) of many of these aldehyde complexes afford O-protonated or O-methylated eta(2)-aldehydium intermediates, respectively, which over time convert to the corresponding carbyne complex. The chemistry of olefin-coordinated alpha,beta-unsaturated aldehyde complexes is also explored.
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收藏
页码:12772 / 12778
页数:7
相关论文
共 41 条
[1]  
[Anonymous], APPL HOMOGENEOUS CAT
[2]   ORGANOMETALLIC MODELS FOR POSSIBLE FISCHER-TROPSCH INTERMEDIATES - SYNTHESIS, STRUCTURE, AND REACTIONS OF A FORMALDEHYDE COMPLEX OF OSMIUM [J].
BROWN, KL ;
CLARK, GR ;
HEADFORD, CEL ;
MARSDEN, K ;
ROPER, WR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (02) :503-505
[3]   SYNTHESIS, STRUCTURE, AND REACTIONS OF (1-ETHOXYETHYL)ZIRCONOCENE CHLORIDE, A STABLE ACYCLIC SECONDARY ZIRCONOCENE ALKYL [J].
BUCHWALD, SL ;
NIELSEN, RB ;
DEWAN, JC .
ORGANOMETALLICS, 1988, 7 (11) :2324-2328
[4]   SYNTHESIS OF (ALKOXYMETHYL)ZIRCONOCENE CHLORIDES - STEREOCHEMISTRY OF CARBON CARBON BOND FORMATION IN A ZIRCONOCENE-WITTIG REARRANGEMENT [J].
BUCHWALD, SL ;
NIELSEN, RB ;
DEWAN, JC .
ORGANOMETALLICS, 1989, 8 (07) :1593-1598
[5]   SYNTHESIS, STRUCTURE, AND REACTIVITY OF THE FORMALDEHYDE COMPLEX [(ETA-5-C5H5)RE(NO)(PPH3)(ETA-2-H2C=O)]+PF6- [J].
BUHRO, WE ;
GEORGIOU, S ;
FERNANDEZ, JM ;
PATTON, AT ;
STROUSE, CE ;
GLADYSZ, JA .
ORGANOMETALLICS, 1986, 5 (05) :956-965
[6]   DEAROMATIZATION OF FURAN - STRUCTURE OF AN ETA(2)-FURAN COMPLEX AND A SURVEY OF ITS REACTIVITY [J].
CHEN, HY ;
HODGES, LM ;
LIU, RG ;
STEVENS, WC ;
SABAT, M ;
HARMAN, WD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (12) :5499-5500
[7]   Dissociative nucleophilic substitution of eta(2)-olefin complexes via a novel eta(2)-vinyl cation intermediate [J].
Chen, HY ;
Harman, WD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (24) :5672-5683
[8]   SYNTHESIS, STRUCTURE AND REACTIONS OF A DIHAPTO-FORMALDEHYDE COMPLEX, OS(ETA-2-CH2O)(CO)2(PPH3)2 [J].
CLARK, GR ;
HEADFORD, CEL ;
MARSDEN, K ;
ROPER, WR .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1982, 231 (04) :335-360
[9]   ETA-2 VERSUS ETA-1 COORDINATION OF ALDEHYDES AND KETONES IN ORGANOMETALLIC COMPLEXES - A SEMIEMPIRICAL THEORETICAL-STUDY [J].
DELBECQ, F ;
SAUTET, P .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (07) :2446-2455
[10]   THE 3-MEMBERED METALLACYCLIC STRUCTURE OF (ETA-5-C5H5)2ZRCL-SUBSTITUTED DIMETHYL ETHER [J].
ERKER, G ;
SCHLUND, R ;
KRUGER, C .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1986, (18) :1403-1404