Reactivity of [Re(η2-H2)(CO)2P3]+ cations with alkynes:: preparation of vinylidene and propadienylidene complexes

被引:21
作者
Albertin, G [1 ]
Antoniutti, S [1 ]
Bordignon, E [1 ]
Bresolin, D [1 ]
机构
[1] Univ Venice, Dipartimento Chim, I-30123 Venice, Italy
关键词
rhenium; hydride; vinylidene; acetylide; propadienylidene;
D O I
10.1016/S0022-328X(00)00020-6
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Treatment of [Re(eta(2)-H-2(CO)(2)P-3](+) cations with phenylacetylene leads to the displacement of H-2 and the formation of vinylidene [Re{C=C(H)Ph}(CO)(2)P-3](+) (1-3) [P = P(OEt)(3), PPh(OEt)(2) or PPh2OEt] derivatives. Infrared and NMR data support equilibrium in solution [Re(CO)(2)P-3](+) + PhC=H reversible arrow [Re{=C=C(H)Ph}(CO)(2)P-3](+) involving the unsaturated complex, free alkyne and vinylidene derivative. 1,4-Diethynylbenzene also tautomerises to the Re(I) centre, affording the [Re{=C=C(PI)(1,4-C6H4C=CH)}(CO)(2)P-3]BF4 [P = P(OEt)(3) or PPh(OEt)(2)] vinylidene derivatives. Vinylidene complexes 1-3 are deprotonated easily by NEt3 to give acetylides Re(C=CR)(CO)(2)P-3 (4-6) (R=Ph or 1,4-C6H4C=CH), which may in turn be reprotonated with HBF4. Et2O to reform vinylidenes 1-3. Acetylide complexes 4-6 were also prepared by reacting unsaturated cations [Re(CO)(2)P-3](+) with lithium acetylide. Binuclear complexes {Re(CO)(2)P-3}(2)(mu-1,4-C=CC6H4C=C) (7, 8) [P = PPh(OEt)(2) or PPh2OEt] were obtained by sequential treatment of [Re(CO)(2)P-3](+) cations, first with 1,4-HC=CC6H4C=CH and then with an excess of NEt3. Propadienylidene complexes [Re(=C=C=CPh2)(CO)(2)P-3]BF4 (9, 10) [P=PPh(OEt)(2) or PPh2OEt] were prepared by allowing[Re(eta(2)-H-2)(CO)(2)P-3](+) cations or unsaturated species [Re(CO)(2)P-3](+) to react with HC=CC(Ph-2)OH at room temperature. The characterisation of all new complexes by IR and H-1-, P-31{H-1}- and C-13{H-1}-NMR spectra is also discussed. (C) 2000 Elsevier Science S.A. All rights reserved.
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页码:10 / 20
页数:11
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共 63 条
[1]   REACTIONS OF MOLECULAR-HYDROGEN COMPLEXES [RUH(ETA-2-H2)P4]BF4 WITH ALKYNES - PREPARATION AND CRYSTAL-STRUCTURE OF THE [RU(ETA-3-(PARA-TOLYL)C3CH(PARA-TOLYL))(PHP(OET)2)4]BPH4 DERIVATIVE [J].
ALBERTIN, G ;
AMENDOLA, P ;
ANTONIUTTI, S ;
IANELLI, S ;
PELIZZI, G ;
BORDIGNON, E .
ORGANOMETALLICS, 1991, 10 (08) :2876-2883
[2]   REACTIVITY OF IRON(II) NONCLASSICAL HYDRIDES WITH ALKYNES [J].
ALBERTIN, G ;
ANTONIUTTI, S ;
DELMINISTRO, E ;
BORDIGNON, E .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (22) :3203-3208
[3]   Preparation of new acetylide and vinylidene complexes of ruthenium [J].
Albertin, G ;
Antoniutti, S ;
Bordignon, E ;
Granzotto, M .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1999, 585 (01) :83-92
[4]   BIS(ALKYNYL) AND ALKYNYL-VINYLIDENE IRON(LL) COMPLEXES WITH MONODENTATE PHOSPHITE LIGANDS [J].
ALBERTIN, G ;
ANTONIUTTI, S ;
BORDIGNON, E ;
DELMINISTRO, E ;
IANELLI, S ;
PELIZZI, G .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1995, (11) :1783-1789
[5]   Preparation, characterisation and reactivity of a series of classical and non-classical rhenium hydride complexes [J].
Albertin, G ;
Antoniutti, S ;
Garcia-Fontan, S ;
Carballo, R ;
Padoan, F .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1998, (12) :2071-2081
[6]   SYNTHESIS AND CHARACTERIZATION OF ENYNYL, VINYL AND ACETYLIDE COMPLEXES OF OSMIUM(II) [J].
ALBERTIN, G ;
ANTONIUTTI, S ;
BORDIGNON, E .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1995, (05) :719-725
[7]   PREPARATION, STRUCTURE, AND REACTIVITY OF NEW BIS(ACETYLIDE) AND ACETYLIDE-VINYLIDENE RUTHENIUM(II) COMPLEXES STABILIZED BY PHOSPHITE LIGANDS [J].
ALBERTIN, G ;
ANTONIUTTI, S ;
BORDIGNON, E ;
CAZZARO, F ;
IANELLI, S ;
PELIZZI, G .
ORGANOMETALLICS, 1995, 14 (09) :4114-4125
[8]   POLYMERS WITH COMPLEXED CYCLOBUTADIENE UNITS IN THE MAIN-CHAIN - THE FIRST EXAMPLE OF A THERMOTROPIC, LIQUID-CRYSTALLINE ORGANOMETALLIC POLYMER [J].
ALTMANN, M ;
BUNZ, UHF .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1995, 34 (05) :569-571
[9]   SWAN-MR - A COMPLETE AND EXPANSIBLE NMR SOFTWARE FOR THE MACINTOSH [J].
BALACCO, G .
JOURNAL OF CHEMICAL INFORMATION AND COMPUTER SCIENCES, 1994, 34 (06) :1235-1241
[10]   New forms of coordinated carbon:: Wirelike cumulenic C3 and C5 sp carbon chains that span two different transition metals and mediate charge transfer [J].
Bartik, T ;
Weng, WQ ;
Ramsden, JA ;
Szafert, S ;
Falloon, SB ;
Arif, AM ;
Gladysz, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (43) :11071-11081