Catalytic hydroarylation of olefins promoted by dicationic Platinum(II) and Palladium(II) complexes. The interplay of C-C bond formation and M-C bond cleavage

被引:33
作者
Cucciolito, Maria Elena [1 ]
D'Amora, Angela [1 ]
Tuzi, Angela [1 ]
Vitagliano, Aldo [1 ]
机构
[1] Univ Naples Federico II, Dipartimento Chim Paolo Corradini, Complesso Univ Monte S Angelo, I-80126 Naples, Italy
关键词
D O I
10.1021/om700692s
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The coordinated olefin in dicationic platinum(II) and palladium(II) complexes [M(PNP)(olefin)](SbF6)(2) (M = Pt, Pd; PNP = 2,6-bis(diphenylphosphinomethyl)pyridine; olefin = ethene, propene) is electrophilic enough to react with benzene rings activated by methoxy substituents. If the proton released by the aromatic ring is trapped by a base, stable sigma-alkyl derivatives of the type [M(PNP)CH2CH(R)Ar](SbF6) or [M(PNP)CH(R)CH2Ar](SbF6) (R = H, Me) are formed; otherwise the M-C sigma-bond can be cleaved by the proton, setting up a catalytic cycle that leads to the alkylated aromatic compound. The molecular structure of the sigma-alkyl derivative [(PNP)PtCH2CH2-C6H2(OMe)(3)](BF4) has been determined by X-ray diffraction analysis, and the factors affecting the mechanism and the rates of the catalytic reaction have been qualitatively investigated and rationalized, showing that the rates of C-C bond formation and M-C bond cleavage are inversely correlated.
引用
收藏
页码:5216 / 5223
页数:8
相关论文
共 29 条
[11]  
Hahn C, 2001, EUR J INORG CHEM, P419
[12]   Coordination of olefins and N-donor ligands at the fragment [2,6-bis((diphenylphosphino)methyl)pyridine]palladium(II).: Synthesis, structure, and amination of the new dicationic complexes [Pd(PNP)(CH2=CHR)](BF4)2 (R=H, Ph) [J].
Hahn, C ;
Vitagliano, A ;
Giordano, F ;
Taube, R .
ORGANOMETALLICS, 1998, 17 (10) :2060-2066
[13]   REACTIONS INVOLVING TRANSITION-METALS .11. REACTIONS OF NUCLEOPHILES WITH DIENE-PLATINUM COMPLEXES [J].
HASZELDINE, RN ;
PARISH, RV ;
ROBBINS, DW .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1976, (22) :2355-2363
[14]   Platinum-based catalysts for the hydroamination of olefins with sulfonamides and weakly basic anilines [J].
Karshtedt, D ;
Bell, AT ;
Tilley, TD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (36) :12640-12646
[15]   Pt-Ag catalyst system for hydroarylations with unactivated arenes and olefins [J].
Karshtedt, D ;
Bell, AT ;
Tilley, TD .
ORGANOMETALLICS, 2004, 23 (18) :4169-4171
[16]   ENHANCED ELECTROPHILICITY OF COORDINATED ETHYLENE IN A CATIONIC PLATINUM(II) COMPLEX [J].
MARESCA, L ;
NATILE, G .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1983, (01) :40-41
[17]   STABLE ETA-ETHENE AND SIGMA-ETHENE CATIONIC COMPLEXES OF PLATINUM(II) [J].
MARESCA, L ;
NATILE, G ;
RIZZARDI, G .
INORGANICA CHIMICA ACTA-ARTICLES, 1980, 38 (01) :53-57
[18]  
MARESCA L, 1994, COMMENT INORG CHEM, V16, P95
[19]   Room temperature palladium-catalyzed intramolecular hydroamination of unactivated alkenes [J].
Michael, FE ;
Cochran, BM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (13) :4246-4247
[20]  
NONIUS BV, 1997, COLL DAT COLL SOFTW