Issue 23, 2005

Bis(isothiocyanato)bis(phosphine) complexes of group 10 metals: reactivity toward organic isocyanides

Abstract

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–µ-NCS)(NCS)3]22− (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.

Graphical abstract: Bis(isothiocyanato)bis(phosphine) complexes of group 10 metals: reactivity toward organic isocyanides

Supplementary files

Article information

Article type
Paper
Submitted
09 Jun 2005
Accepted
15 Aug 2005
First published
08 Sep 2005

Dalton Trans., 2005, 3722-3731

Bis(isothiocyanato)bis(phosphine) complexes of group 10 metals: reactivity toward organic isocyanides

X. Chang, K. Lee, S. Il Jeon, Y. Kim, H.-K. Lee and S. W. Lee, Dalton Trans., 2005, 3722 DOI: 10.1039/B508134C

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements