The First Metathesis of C-C Single Bonds in Homogeneous Solution: Titanocene-Mediated and Photocatalyzed Cleavage and Recombination of Disubstituted Butadiynes
The First Metathesis of C-C Single Bonds in Homogeneous Solution: Titanocene-Mediated and Photocatalyzed Cleavage and Recombination of Disubstituted Butadiynes
Synthese von [(η5-C5H5)2Ti(Cl)(CCSiMe3)]Ni(CO) und dessen Reaktionsverhalten gegenüber Phosphiten: die Festkörperstruktur von (CO)2Ni[P(OC6H4CH3-2)3]2
作者:E Meichel、Th Stein、J Kralik、G Rheinwald、H Lang
DOI:10.1016/s0022-328x(02)01117-8
日期:2002.4
Treatment of [Ti](Cl)(CCSiMe3) (1) [Ti]=(η5-C5H5)2Ti} with Ni(CO)4 (2) in a 1:1 molar ratio produces the heterobimetallic early–late transition metal complex [Ti](Cl)(CCSiMe3)}Ni(CO) (3), which features a low-valent Ni(CO) entity stabilized by a datively bonded Cl and a η2-coordinated Me3SiCC ligand. As side-products [Ti]Cl2 (8) and [Ti](CCSiMe3)2}Ni(CO) (5) are formed. The latter complex can
钛[Ti](CL)(CCSiMe的处理3)(1)[钛] =(η 5 -C 5 H ^ 5)2的Ti}用Ni(CO)4(2在1):1的摩尔比产生的异早迟过渡金属络合物钛[Ti](CL)(CCSiMe 3)}的Ni(CO)(3),其设有由datively接合Cl和稳定的低原子价的Ni(CO)实体η 2配位的我3 SiCC配体。作为副产物钛[Ti]氯2(8)和[钛](CCSiMe 3)2 }的Ni(CO)(5) 形成。后者复杂也可以通过钛[Ti](CCSiMe反应合成3)2(4)与等摩尔量的2。如果3与化学计算量的P(OR)3(6a,R = C 6 H 5 ; 6b,R = C 6 H 4 CH 3 -2; 6c,R = C 6 H 4 t Bu-2)反应,则双(炔基)钛茂4,(CO)2 Ni [P(OR)3 ] 2(7a,R = C6 H 5;7b,R = C 6 H 4 CH
The First Metathesis of C-C Single Bonds in Homogeneous Solution: Titanocene-Mediated and Photocatalyzed Cleavage and Recombination of Disubstituted Butadiynes
作者:Siegmar Pulst、Frank G. Kirchbauer、Barbara Heller、Wolfgang Baumann、Uwe Rosenthal