Stepwise successive insertion of carbon monoxide and allenes into palladium-carbon bonds of complexes containing the rigid bidentate nitrogen ligand bis(p-anisylimino)acenaphthene

被引:93
作者
Groen, JH
Elsevier, CJ
Vrieze, K
Smeets, WJJ
Spek, AL
机构
[1] UNIV AMSTERDAM,ANORGAN CHEM LAB,JH VANT HOFF RES INST,NL-1018 WV AMSTERDAM,NETHERLANDS
[2] UNIV UTRECHT,BIJVOET CTR BIOMOL RES,LAB KRISTAL & STRUCT CHEM,NL-3584 CH UTRECHT,NETHERLANDS
关键词
D O I
10.1021/om960163p
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Propadiene, 3-methyl-1,2-butadiene (DMA), and 2,4-dimethyl-2,3-pentadiene (TMA) reacted via migratory insertion with both neutral and ionic Pd(R)X(p-An-BIAN) (R = Me (1), C(O)Me (2); X = Cl (a), SO3CF3 (b)) complexes, containing the rigid nitrogen ligand bis(p-anisylimino)acenaphthene (p-An-BIAN), resulting in the novel and stable allylpalladium complexes Pd(eta(3)-C(3)H(4)R)X(p-An-BIAN) (R = Me (3), C(O)Me (6)), Pd(eta(3)-C(5)H(8)R)X(p-An-BIAN) (R = Me (4), C(O)Me (7)), and Pd(eta(3)-C(7)H(12)R)X(p-An-BIAN) (R = Me (5), C(O)Me (8)), respectively (X = Cl (a), SO3CF3 (b)). The neutral complexes 6a and 7a reacted with carbon monoxide to form the acylpalladium complexes Pd(C(O)C3H4C(O)Me)Cl(p-An-BIAN) (9) and Pd(C(O)C5H8C(O)Me)Cl(p-An-BIAN) (10), respectively, while the analogous trifluoromethanesulfonate complexes 6b and 7b were completely inert toward CO. Complexes 9 and 10 reacted again with propadiene and DMA, respectively, to yield the allylpalladium complexes Pd(eta(3)-C3H4C(O)C3H4C(O)Me)Cl(p-An-BIAN) (11) and Pd(eta(3)-C5H8C(O)C5H8C(O)Me)Cl(p-An-BIAN) (12), respectively. Also insertion of norbornadiene in complex 10 was possible, yielding the ionic complex [Pd(C7H8C(O)C5H8C(O)Me)(p-An-BIAN)]Cl (13a), which reacted with AgSO3CF3 to give [Pd(C7H8C(O)C5H8C(O)Me)(p-An-BIAN)]SO3CF3 (13b). The novel complexes 9-12 are the first isolated and fully characterized complexes formed by successive insertion reactions of carbon monoxide and allenes, while 13a is the first isolated complex containing a metal-bonded ter-oligomer of carbon monoxide, an allene, and norbornadiene. The X-ray crystal structure of 7a has been determined and shows a distorted square pyramidal geometry in which the BIAN ligand is bonded to the palladium center in an unusual asymmetric fashion (Pd-N(1)= 2.144(7) Angstrom; Pd-N(2)= 2.600(8) Angstrom).
引用
收藏
页码:3445 / 3455
页数:11
相关论文
共 60 条
[1]   2D NOESY OF PALLADIUM PI-ALLYL COMPLEXES - REPORTER LIGANDS, COMPLEX DYNAMICS, AND THE X-RAY STRUCTURE OF [PD(ETA-3-C4H7)(BPY)](CF3SO3) (BPY = BIPYRIDINE) [J].
ALBINATI, A ;
KUNZ, RW ;
AMMANN, CJ ;
PREGOSIN, PS .
ORGANOMETALLICS, 1991, 10 (06) :1800-1806
[2]   CARBONYL-INSERTION REACTIONS OF SQUARE-PLANAR COMPLEXES [J].
ANDERSON, GK ;
CROSS, RJ .
ACCOUNTS OF CHEMICAL RESEARCH, 1984, 17 (02) :67-74
[3]   EFFECTS OF STEREOCHEMISTRY AT PLATINUM AND THE NATURE OF THE ORGANIC GROUP ON CARBONYL INSERTION AT [PTCL(R)(CO)(PMEPH2)] [J].
ANDERSON, GK ;
CROSS, RJ .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1979, (07) :1246-1250
[4]  
ANKERSMIT HA, IN PRESS INORG CHIM
[5]   ENANTIOSELECTIVE ISOTACTIC ALTERNATING COPOLYMERIZATION OF STYRENE AND 4-METHYLSTYRENE WITH CARBON-MONOXIDE CATALYZED BY A CATIONIC BIOXAZOLINE PD(II) COMPLEX [J].
BARTOLINI, S ;
CARFAGNA, C ;
MUSCO, A .
MACROMOLECULAR RAPID COMMUNICATIONS, 1995, 16 (01) :9-14
[6]   MECHANISTIC ASPECTS OF THE ALTERNATING COPOLYMERIZATION OF CARBON-MONOXIDE WITH OLEFINS CATALYZED BY CATIONIC PALLADIUM COMPLEXES [J].
BATISTINI, A ;
CONSIGLIO, G .
ORGANOMETALLICS, 1992, 11 (05) :1766-1769
[7]   PALLADIUM-CATALYZED REACTION OF BUTADIENE AND CARBON-DIOXIDE [J].
BEHR, A ;
JUSZAK, KD .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1983, 255 (02) :263-268
[8]  
BEURSKENS PT, 1992, DIRDIF PROGRAM SYSTE
[9]   PALLADIUM(II) CATALYSTS FOR LIVING ALTERNATING COPOLYMERIZATION OF OLEFINS AND CARBON-MONOXIDE [J].
BROOKHART, M ;
RIX, FC ;
DESIMONE, JM ;
BARBORAK, JC .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (14) :5894-5895
[10]   INSERTION OF OLEFINS INTO PALLADIUM(II)-ACYL BONDS - MECHANISTIC AND STRUCTURAL STUDIES [J].
BRUMBAUGH, JS ;
WHITTLE, RR ;
PARVEZ, M ;
SEN, A .
ORGANOMETALLICS, 1990, 9 (06) :1735-1747