Thomas DANIEL, Hirotaka NAGAO, Hiroshi NAKAJIMA, Koji TANAKA and Akira NAKAMURA
[J. Organometallic Chem. 509, 225 (1996)]
A norbornadiene(terpyridine) complex [Mo(CO)-(C7H8)(terpy)I]I (2a) was prepared in two steps from [Mo(CO)4(C7H8)] (1), iodine and 2,2' : 6',2"-terpyridine. On treatment with either KPF6 in methanol or AgSbF6 in CH2Cl2 the more soluble salts [Mo(CO)-(C7H8)(terpy)I]PF6 (2b) and [Mo(CO)(C7H8)(terpy)I]-SbF6 (2c) were isolated with good yields. With 4,4',4"-tri-tert-butyl-2,2' : 6',2"-terpyridine, in similar reactions the tert-butyl-substituted terpyridine compounds [Mo(CO)(C7H8)(4,4',4"-tBu3terpy)I]X (X = I (3a), PF6 (3b) or SbF6 (3c)) were obtained, while the oxidation of 1 with two equiv of CuBr2 led to the bromo-(terpyridine) complexes [Mo(CO)(C7H8)(terpy)Br]X (X = Br (4a), PF6 (4b) or SbF6 (4c)). The X-ray structural analysis for 4c revealed a triangle formed by the norbonadiene and the halogen is perpendicular to the plane formed by terpyridine and CO. The iodo compound 2a and the bromo analogue 4a reacted with two equiv of AgSbF6 to give a complex of the composition {[Mo(CO)(C7H8)(terpy)]2(acetone)}-(SbF6)4 (5). Treatment of 5 with two equiv of PMe3 afforded [Mo(CO)(C7H8)(terpy)PMe3](SbF6)2·acetone (6). The similar compound [Mo(CO)(C7H8)(terpy)-NCCH2CH3](SbF6)2 (7), which can be easily prepared from 5 and a fivefold excess of propionitrile.