Synthesis and reactivity of indenyl ruthenium(II) complexes containing the labile ligand 1,5-cyclooctadiene (COD):: Catalytic activity of [Ru(η5-C9H7)Cl(COD)]

被引:66
作者
Alvarez, P
Gimeno, J [1 ]
Lastra, E
García-Granda, S
Van der Maelen, JF
Bassetti, M
机构
[1] Univ Oviedo, Dept Quim Organ & Inorgan, Fac Quim, Inst Quim Enrique Moles,Unidad Asociada CSIC, E-33006 Oviedo, Spain
[2] Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, E-33006 Oviedo, Spain
[3] Univ Roma La Sapienza, Ctr Studio Meccanismi Reaz, CNR, Dipartimento Chim, I-00185 Rome, Italy
关键词
D O I
10.1021/om010205w
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The treatment of [RuCl2(COD)](n) with KC9H7 in THF leads to the formation of [Ru(eta (5)-C9H7)Cl(COD)] (1) (80% yield) in a one-pot synthesis. Complex 1 is also formed by the reaction of [RuCl2(COD)](n) with NaC9H7 in THF followed by treatment of the intermediate complex [Ru(eta (5)-C9H7)(eta (2)-eta (3)-C8H11)] (2) with HCL Substitution of the labile COD ligand by bulky phosphines PR3 (R = Cy, Pr-i(3)) can be achieved at room temperature in THF to give 16-electron species [Ru(eta (5)-C9H7)Cl(PR3)], which react with CO (1 atm) to afford complexes [Ru(eta (5)-C9H7)Cl(CO)(PR3)] (R = Cy (3a), Pr-i (3b)). Chelate complexes [Ru(eta (5)-C9H7)Cl{(kappa (2)-P,N)-o-Ph2PC6H4C(H)=(NBu)-Bu-t}] (4) and [Ru(eta (4)-C9H7){kappa (1)-(P)-Ph2PCH2C(O)Bu-t}{kappa (2)-(P,O)Ph2PCH= C(O)Bu-t}] (5) have been similarly prepared by reaction with the bidentate ligands. [Ru(eta (5)-C9H7)Cl(NBD)] (NBD = norbornadiene) (6) has been prepared through an exchange reaction of 1 with NBD and characterized by X-ray diffraction. Neutral complexes [Ru(eta (5)-C9H7)X-(COD)] (X = FBF3 (7), N-3 (8)) were prepared from complex 1 by metathesis reactions of the chloride ligand by AgBF4 and NaN3 respectively. The treatment of 7 in CH2Cl2 with an excess of pyridine and acetonitrile gives cationic complexes [Ru(eta (5)-C9H7)(COD)L] [BF4] in good yield (L = py (9), CH3CN (10)). The structure of complex 9 has been determined by X-ray diffraction. Complex 1 catalyzes [2+2] and [4+2] cycloaddition reactions of norbornene and 1,5-cyclooctadiene with alkynes to give exotricyclic [4.2.1.0] coupling products and exotricyclo [4.2.2.0]dec-7-enes, respectively. These processes take place with high efficiency and selectivity. Complex I is also active in the catalytic hydration of terminal alkynes to afford ketones in high yield and selectivity.
引用
收藏
页码:3762 / 3771
页数:10
相关论文
共 96 条
[31]   Synthesis of ruthenium(II) 1,2,3-trimethylindenyl complexes: X-ray crystal structure of [Ru(=C=C=CPh2)(eta(5)-1,2,3-Me3C9H4)(CO)(PPh3)][BF4] [J].
Gamasa, MP ;
Gimeno, J ;
GonzalezBernardo, C ;
Borge, J ;
GarciaGranda, S .
ORGANOMETALLICS, 1997, 16 (12) :2483-2485
[32]   Phosphine substitution in indenyl- and cyclopentadienylruthenium complexes. Effect of the eta(5) ligand in a dissociative pathway [J].
Gamasa, MP ;
Gimeno, J ;
GonzalezBernardo, C ;
MartinVaca, BM ;
Monti, D ;
Bassetti, M .
ORGANOMETALLICS, 1996, 15 (01) :302-308
[33]   Ruthenium tris(pyrazolyl)borate complexes .1. Synthesis and reactivity of Ru(HB(pz)(3))(COD)X (X=Cl, Br) and Ru(HB(pz)(3))(L(2))Cl (L=nitrogen and phosphorus donor ligands) [J].
Gemel, C ;
Trimmel, G ;
Slugovc, C ;
Kremel, S ;
Mereiter, K ;
Schmid, R ;
Kirchner, K .
ORGANOMETALLICS, 1996, 15 (19) :3998-4004
[34]   Synthesis and reactivity of [Ru{HB(pz)(3)}{P(C6H11)(3)}Cl(OCH2R)] (pz equals pyrazolyl, R=H or Me) [J].
Gemel, C ;
Kickelbick, G ;
Schmid, R ;
Kirchner, K .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1997, (12) :2113-2117
[35]   RHODIUM IMINOPHOSPHINE COMPLEXES AS EFFICACIOUS OXYGEN CARRIERS - CRYSTAL-STRUCTURE OF A REPRESENTATIVE DIOXYGEN ADDUCT [J].
GHILARDI, CA ;
MIDOLLINI, S ;
MONETI, S ;
ORLANDINI, A ;
SCAPACCI, G .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (23) :3371-3376
[36]  
GIMENO J, UNPUB
[37]   ANALYSIS OF SINGLE-CRYSTAL BRAGG-REFLECTIONS FROM PROFILE MEASUREMENTS [J].
GRANT, DF ;
GABE, EJ .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1978, 11 (APR) :114-120
[38]  
HALL SR, 1995, XTAL GX PACKAGE MANU
[39]   FORMATION AND PROPERTIES OF SOME CHLORACARBONYL COMPLEXES OF RUTHENIUM (2) AND RUTHENIUM(3) [J].
HALPERN, J ;
JAMES, BR ;
KEMP, ALW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1966, 88 (22) :5142-&
[40]   CATALYSIS OF HYDRATION OF ACETYLENIC COMPOUNDS BY RUTHENIUM(III) CHLORIDE [J].
HALPERN, J ;
JAMES, BR ;
KEMP, ALW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1961, 83 (19) :4097-&