TY - JOUR
T1 - Reactions of α-diimine-stabilized Zn-Zn-bonded compounds with phenylacetylene
AU - Gao, Jing
AU - Li, Shaoguang
AU - Zhao, Yanxia
AU - Wu, Biao
AU - Yang, Xiao Juan
PY - 2012/4/23
Y1 - 2012/4/23
N2 - Treatment of the Zn-Zn-bonded compounds [L 2-Zn-ZnL 2-]· [M(THF) 2] 2 (1a, M = Na; 1b, M = K; L = [(2,6-iPr 2C 6H 3)NC(Me)] 2), which contain doubly reduced α-diimine ligands, with 15-crown-5 and 18-crown-6 led to the ion-separated compounds [L 2-Zn-ZnL 2-]· [Na(15-crown-5)(THF) 2] 2 (2a), [L 2-Zn-ZnL 2-]· [K(15-crown-5) 2] 2·4THF (2b), and [L 2-Zn-ZnL 2-]· [K(18-crown-6)(THF) 2] 2·2THF (2c). In the products, the alkali metal ions originally bound by the ligands have been captured by the crown ethers. The Zn-Zn bond distances in 2a, 2b, and 2c are longer than those in the corresponding parent compounds 1a and 1b and in an analogous compound, [L -Zn-ZnL -] (3), bearing the monoanionic α-diimine ligands. Theoretical computations suggested that the Zn-Zn bonds in 2a-c are less stable than those in 1a and 1b. Reactions of [L -Zn-ZnL -] (3) with different amounts of PhC≡CH afforded the dimeric product [L -Zn(ν-C≡CPh)] 2 (4) and the monomeric [L 0Zn(C≡CPh) 2]·2THF (5), respectively, while the reaction of the crown ether-containing compound 2b with PhC≡CH gave a homoleptic zinc alkynide, [Zn(C≡CPh) 4]·[K(15-crown-5) 2] 2·THF (6).
AB - Treatment of the Zn-Zn-bonded compounds [L 2-Zn-ZnL 2-]· [M(THF) 2] 2 (1a, M = Na; 1b, M = K; L = [(2,6-iPr 2C 6H 3)NC(Me)] 2), which contain doubly reduced α-diimine ligands, with 15-crown-5 and 18-crown-6 led to the ion-separated compounds [L 2-Zn-ZnL 2-]· [Na(15-crown-5)(THF) 2] 2 (2a), [L 2-Zn-ZnL 2-]· [K(15-crown-5) 2] 2·4THF (2b), and [L 2-Zn-ZnL 2-]· [K(18-crown-6)(THF) 2] 2·2THF (2c). In the products, the alkali metal ions originally bound by the ligands have been captured by the crown ethers. The Zn-Zn bond distances in 2a, 2b, and 2c are longer than those in the corresponding parent compounds 1a and 1b and in an analogous compound, [L -Zn-ZnL -] (3), bearing the monoanionic α-diimine ligands. Theoretical computations suggested that the Zn-Zn bonds in 2a-c are less stable than those in 1a and 1b. Reactions of [L -Zn-ZnL -] (3) with different amounts of PhC≡CH afforded the dimeric product [L -Zn(ν-C≡CPh)] 2 (4) and the monomeric [L 0Zn(C≡CPh) 2]·2THF (5), respectively, while the reaction of the crown ether-containing compound 2b with PhC≡CH gave a homoleptic zinc alkynide, [Zn(C≡CPh) 4]·[K(15-crown-5) 2] 2·THF (6).
UR - http://www.scopus.com/inward/record.url?scp=84860329353&partnerID=8YFLogxK
U2 - 10.1021/om200868j
DO - 10.1021/om200868j
M3 - Article
AN - SCOPUS:84860329353
SN - 0276-7333
VL - 31
SP - 2978
EP - 2985
JO - Organometallics
JF - Organometallics
IS - 8
ER -