Nishimura Yoshimasa, Arikawa Yasuhiro, Inoue Takanori, Onishi Masayoshi
Department of Applied Chemistry, Faculty of Engineering, Nagasaki University, Bunkyo-machi 1-14, Nagasaki, 852-8521, Japan.
Dalton Trans. 2005 Mar 7(5):930-7. doi: 10.1039/b415483e. Epub 2005 Feb 2.
A nitrosylruthenium alkynyl complex of TpRuCl(C[triple bond]CPh)(NO)(1a) was reacted with PPh3 in the presence of HBF4.Et2O at room temperature to give a beta-phosphonio-alkenyl complex (E)-[TpRuCl{CH=C(PPh3)Ph}(NO)]BF4(2.BF4). On the other hand, for gamma-hydroxyalkynyl complexes TpRuCl{C[triple bond]CC(R)2OH}(NO)(R = Me (1b), Ph (1c), H (1d)), similar treatments with PPh3 were found to give gamma-phosphonio-alkynyl [TpRuCl{C[triple bond]CC(Me)2PPh3}(NO)]BF4(3.BF4),alpha-phosphonio-allenyl [TpRuCl{C(PPh3)=C=CPh2}(NO)]BF4(4.BF4), and a novel product of gamma-hydroxy-beta-phosphonio-alkenyl (E)-[TpRuCl{CH=C(PPh3)CH2OH}(NO)]BF4(5.BF4), respectively. Dominant factors for the selectivity in affording 3-5 were associated with the steric congestion and electronic properties at the gamma-carbons, along with those around the metal fragment. From the bis(alkynyl) complex TpRu(C[triple bond]CPh)2(NO)6, a bis(beta-phosphonio-alkenyl)(E,E)-TpRu{CH=C(PPh3)Ph}2(NO)2{7.(BF4)2} was produced at room temperature. However, similar reactions at 0 degrees C gave an alkynyl beta-phosphonio-alkenyl complex (E)-[TpRu(C[triple bondCPh){CH=C(PPh3)Ph}(NO)]BF4(8.BF4) as a sole product, of which additional hydration in the presence of HBF4.Et2O afforded a [small beta]-phosphonio-alkenyl ketonyl (E)-[TpRu{CH2C(O)Ph}{CH=C(PPh3)Ph}(NO)]BF(.9BF4). Five complexes, 2-5 and 7 were crystallographically characterized.
在室温下，将三苯基膦钌炔基配合物TpRuCl(C≡CPh)(NO)(1a)与PPh₃在HBF₄·Et₂O存在下反应，得到β-膦酰基-烯基配合物(E)-[TpRuCl{CH=C(PPh₃)Ph}(NO)]BF₄(2·BF₄)。另一方面，对于γ-羟基炔基配合物TpRuCl{C≡CC(R)₂OH}(R = Me (1b)、Ph (1c)、H (1d))，发现用PPh₃进行类似处理分别得到γ-膦酰基-炔基配合物[TpRuCl{C≡CC(Me)₂PPh₃}(NO)]BF₄(3·BF₄)、α-膦酰基-联烯基配合物[TpRuCl{C(PPh₃)=C=CPh₂}(NO)]BF₄(4·BF₄)和一种新型产物γ-羟基-β-膦酰基-烯基配合物(E)-[TpRuCl{CH=C(PPh₃)CH₂OH}(NO)]BF₄(5·BF₄)。生成3 - 5的选择性的主要因素与γ-碳原子处的空间拥挤和电子性质以及金属片段周围的因素有关。由双(炔基)配合物TpRu(C≡CPh)₂(NO)₆在室温下制得双(β-膦酰基-烯基)(E,E)-TpRu{CH=C(PPh₃)Ph}₂(NO)₂{7·(BF₄)₂}。然而，在0℃下进行类似反应得到炔基β-膦酰基-烯基配合物(E)-[TpRu(C≡CPh){CH=C(PPh₃)Ph}(NO)]BF₄(8·BF₄)作为唯一产物，在HBF₄·Et₂O存在下对其进行额外水合得到β-膦酰基-烯基酮基配合物(E)-[TpRu{CH₂C(O)Ph}{CH=C(PPh₃)Ph}(NO)]BF₄(9·BF₄)。对2 - 5和7这五种配合物进行了晶体学表征。
