| 16471052 |
Chang X, Lee KE, Jeon SI, Kim YJ, Lee HK, Lee SW: Bis (isothiocyanato) bis (phosphine) complexes of group 10 metals: reactivity toward organic isocyanides. Dalton Trans. 2005 Dec 7;(23):3722-31.
Treatment of Ni (NCS) 2 (PMe2Ph) 2 with organic isocyanides CN-R gave five-coordinate isocyanide Ni (II) complexes, Ni (CN-R)(NCS) 2 (PMe2Ph) 2 (R = C6H3-2,6-Me2 (1), t-Bu (2)). Interestingly, the corresponding reaction of Ni (NCS) 2 (P (n-Pr) 3) 2 with 2 equiv. of CN-t-Bu gave an unusual compound, which exists as an ion pair of the trigonal bipyramidal cation [Ni (P (n-Pr) 3) 2 (CN-t-Bu) 3] 2+ (3) and the dinuclear NCS-bridged anion [Ni (1,3-micro-NCS)(NCS) 3] 2 (2-) (4). In contrast, Pd (NCS) 2 (P (n-Pr) 3) 2 underwent substitution with 2 equiv. of CN-t-Bu to give the four-coordinate mono (isocyanide) Pd (II) complex Pd (NCS)(SCN)(CN-t-Bu)(P (n-Pr) 3) (5) via phosphine dissociation. Reactions of M (NCS) 2L2 (M = Pd, Pt; L = PMe3, PEt3, PMePh2, P (n-Pr) 3) with two equiv. of CN-R (R = t-Bu, i-Pr, C6H3-2,6-Me2) gave the corresponding bis (isocyanide) complexes [M (CN-R) 2 (PR3) 2](SCN) 2 (7-13), except for Pd (NCS) 2 (PEt3) 2 that reacted with CN-R' (R' = i-Pr, C6H3-2,6-Me2) and produced the mono (isocyanide) Pd (II) complexes [Pd (CN-R')(SCN)(PEt3) 2](SCN) (14 and 15). Finally, treatment of M (NCS) 2 (PMe3) 2 (M = Ni, Pd, Pt) with sterically bulky isocyanide CN-C6H3-2,6-i-Pr2 gave various products, (16-18) depending on the identity of the metal. |
33(0,1,1,3) |