钴络合共轭二炔盐：一类刚性掩蔽亲电试剂。合成、结构及双亲核取代反应

Cobalt-complexed conjugated diyne salts: a family of rigid masked dielectrophiles. Syntheses, structures, and double nucleophilic substitutions.

作者信息

Amouri H, Da Silva C, Malézieux B, Andrés R, Vaissermann J, Gruselle M

机构信息

Laboratoire de Chimie Inorganique et Matériaux Moléculaires, Unité de Recherche 7071-CNRS, Université Pierre et Marie Curie, Paris, France.

出版信息

Inorg Chem. 2000 Oct 30;39(22):5053-8. doi: 10.1021/ic991433+.

DOI:10.1021/ic991433+

PMID:11233202

Abstract

A family of dicationic diyne salts of the general formula [(Co2(CO)6)2-mu,eta2,eta2-(Nu-CH2C(triple bond)C-C(triple bond)CCH2-Nu)][BF4]2 [Nu = SMe2 (3); Nu = NC6H7, 3-picoline, (5); Nu = NC9H7, quinoline (7)] were prepared and fully characterized. Three X-ray molecular structures of 3, 5, and the neutral starting material 2,4-hexadiyne-1,6-diol complex [(Co2(CO)6)2-mu,eta2,eta2-(HO-CH2C(triple bond)C-C(triple bond)CCH2-OH)] (1) are presented. Complex 1 crystallizes in the triclinic space group P1 with a = 14.722(2) A, b = 14.571(3) A, c = 14.722(2) A, alpha = 105.17(1) degrees, beta = 113.30(1) degrees, gamma = 99.20(1) degrees, and Z = 4. Complex 3 crystallizes in the monoclinic space group P2(1)/n with a = 12.758(3) A, b = 13.360(3) A, c = 20.494(3) A, beta = 91.44(1) degrees, and Z = 4, and compound 5 also crystallizes in the monoclinic space group P2(1)/n with a = 9.426(2) A, b = 21.739(5) A, c = 18.704(3) A, beta = 94.86(1) degrees, and Z = 4. The X-ray structures provide us with valuable information on the arrangement of the Co2-alkyne units, which have a cis geometry and are in sharp contrast to that observed generally for diyne-tetracobalt compounds. Complex [(Co2(CO)6)2-mu,eta2,eta2-(Me2S-CH2C(triple bond)C-C(triple bond)CCH2-SMe2)][BF4]2 (3) reacts with N-, S-, and P-centered nucleophiles and affords the related substituted complexes in high yields. The stability and reactivity of the disulfonium diyne complex 3 toward nucleophiles are compared to those of the analogous disulfonium-yne complex [(Co2(CO)6)2-mu,eta2,eta2-(Me2S-CH2-C(triple bond)C-CH2-SMe2)][BF4]2 (4).

摘要

制备并全面表征了通式为[(Co2(CO)6)2-μ,η2,η2-(Nu-CH2C（三键）C-C（三键）CCH2-Nu)][BF4]2的双阳离子二炔盐家族[Nu = SMe2 (3)；Nu = NC6H7，3-甲基吡啶，(5)；Nu = NC9H7，喹啉 (7)]。给出了3、5以及中性起始原料2,4-己二炔-1,6-二醇配合物[(Co2(CO)6)2-μ,η2,η2-(HO-CH2C（三键）C-C（三键）CCH2-OH)] (1)的三个X射线分子结构。配合物1在三斜空间群P1中结晶，a = 14.722(2) Å，b = 14.571(3) Å，c = 14.722(2) Å，α = 105.17(1)°，β = 113.30(1)°，γ = 99.20(1)°，Z = 4。配合物3在单斜空间群P2(1)/n中结晶，a = 12.758(3) Å，b = 13.360(3) Å，c = 20.494(3) Å，β = 91.44(1)°，Z = 4，化合物5也在单斜空间群P2(1)/n中结晶，a = 9.426(2) Å，b = 21.739(5) Å，c = 18.704(3) Å，β = 94.86(1)°，Z = 4。X射线结构为我们提供了关于Co2-炔单元排列的有价值信息，这些单元具有顺式几何构型，与二炔-四钴化合物通常观察到的情况形成鲜明对比。配合物[(Co2(CO)6)2-μ,η2,η2-(Me2S-CH2C（三键）C-C（三键）CCH2-SMe2)][BF4]2 (3)与以N、S和P为中心的亲核试剂反应，并以高产率得到相关的取代配合物。将二硫鎓二炔配合物3对亲核试剂的稳定性和反应性与类似的二硫鎓-炔配合物[(Co2(CO)6)2-μ,η2,η2-(Me2S-CH2-C（三键）C-CH2-SMe2)][BF4]2 (4)进行了比较。