Reaction of an (alkyl)(alkenyl)(alkynyl)iridium(III) complex with HCl:: Intramolecular C-C bond formation from alkyl, alkenyl, and alkynyl groups coordinated to "'Ir(CO)(PPh3)2".: H/D exchange between CH3 and DCl

被引：27

作者：

Chin, CS ^{[1
]}

Cho, H ^{[1
]}

Won, G ^{[1
]}

Oh, M ^{[1
]}

Ok, KM ^{[1
]}

机构：

[1] Sogang Univ, Dept Chem, Seoul 121742, South Korea

来源：

ORGANOMETALLICS | 1999年 / 18卷 / 23期

关键词：

D O I：

10.1021/om9903442

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Reaction of the (alkyl)(alkenyl)(alkynyl)iridium(III) complex [Ir(CH3)(CH=CHNEt3)(C equivalent to C(p-C6H4CH3))(CO)(PPh3)(2)]ClO4 (3) with aqueous HCl initiates an intramolecular coupling reaction between -CH3 and -C equivalent to C(p-C6H4CH3) groups to give [Ir(C(CH3)=CH(p-C6H4CH3)(CH-CHNEt3)(Cl)(CO)(PPh3)(2)]ClO4 (5), which further reacts with aqueous HCl to produce [Ir(CH=CHNEt3)(Cl)(2)(CO)(PPh3)(2)]ClO4 (6) and cis-CH3CH=CH(p-C6H4CH3) (7).Complex 5 yields the C-C coupling product [(p-C6H4CH3)HC=C(CH3)CH=CHNEt3]ClO4 (8) when it is refluxed in CHCl3. The (alkyl)bis(alkynyl)iridium(III) compound Ir(CH3)(C equivalent to C(p-C6H4CH3))(2)- (CO)(PPh3)(2) (4) reacts with aqueous HCl to give H2C=C=CH(p-C6H4CH3) (9). Complex 3 reacts with excess DCl to give the d(5) isotopomer CD3CD=CD(p-C6H4CH3) (7-d(5)), while the reaction of 4 with DCl gives the d(1) isotopomer H2C=C=CD(p-C6H4CH3) (9-d(1)). Plausible reaction pathways are discussed for the formation of 7 and 9 and for the H/D exchange to give the isotopomer 7-d(5).

引用

页码：4810 / 4816

页数：7

共 65 条

[1] TRANSFORMATION OF THE C2H LIGAND IN FP-ASTERISK-C-EQUIVALENT-TO-CH (FP-ASTERISK=(ETA-5-C5ME5)FE(CO)2) INTO VARIOUS C-2 FUNCTIONAL-GROUPS VIA AN IRON-SUBSTITUTED MANGANESE VINYLIDENE COMPLEX, (ETA-5-C5H4ME)MN(CO)2[=C=C(H)FP-ASTERISK] - ITS AMPHOTERIC REACTIVITIES, STRUCTURAL COMPARISONS RELEVANT TO 1-ALKYNE-TO-VINYLIDENE REARRANGEMENTS, AND ELECTRONIC INFLUENCES ON STRUCTURES OF HETEROBIMETALLIC BRIDGING ALKYNYL COMPLEXES [(ETA-5-C5R5)M(CO)2]2(MU-C2R) [J].