Browse by author
Lookup NU author(s): Mi-Sook Seo, Dr Mark Elsegood, Emeritus Professor Bill CleggORCiD, Emeritus Prof Alfred Sykes
Full text for this publication is not currently held within this repository. Alternative links are provided below where available.
The reaction of Pd black with [Mo3Se4((HO)-O-2)(9)](4+) in 2 M HCl gives the single cube [Mo-3(PdCl)Se-4(H2O)(9)](3+), which on removal of Cl- forms the edge-linked double cube [{Mo3PdSe4(H2O)(9)}(2)](8+). No similar reactions of [W3S4(H2O)(9)](4+) and [W3Se4(H2O)(9)](4+) are observed, and in no case is Pt black incorporated into the trinuclear species. The crystal structure of [{Mo3PdSe4(H2O)(9)}(2)](pts)(8).18H(2)O has been determined (pts(-) = p-toluenesulfonate), and is consistent with Mo-Mo and Mo-Pd bonding. Properties of the Pd derivatives of both [Mo(3)Q(4)(H2O)(9)](4+) (Q = S, Se) are considered. No heteroatom transfer is observed on mixing [Mo-3(PdCl)Se-4(H2O)(9)](3+) with [Mo3S4(H2O)(9)](4+) as is the case of [Mo3SnSe4(H2O)(12)](6+) with [Mo3S4(H2O)(9)](4+). The single cubes [Mo-3(PdCl)Se-4(H2O)(9)](3+) (Q = S, Se), react 1:1 with SnCl3- to give [Mo-3(PdSnCl3)Q(4)(H2O)(9)](3+) with Pd-Sn bonding. Formation constants K (25degreesC) are 1.15 x 10(3) M-1 (Q = S) and 9.5 x 10(3) M-1 (Q = Se). On mixing the heterometal cubes [Mo3PdS4(H2O)(10)](4+) and [Mo3SnS4(H2O)(12)](6+) in 2 M HCl no Pd- Sn bonding occurs. With [Pd(H2O)(4)](2+) and [Mo3SnS4(H2O)(12)](6+) in 2.0 M HClO4, reaction steps Mo3SnS46+-->Mo3S44+ + Sn-II, followed by Sn-II + Pd-II-->Sn-IV + Pd-0 are observed, and Pd-0 is precipitated. Rate constants for the oxidation of [Mo-3(PdCl)S-4(H2O)(9)](4+) and [{Mo3PdS4(H2O)(9)}(2)](8+) with [Co(dipic)(2)](-) (dipic = 2,6-pyridinedicarboxylate) are within a factor of 2, indicating no significant change in redox properties. This contrasts with the behaviour of single and corner-shared double cubes e. g. M' = Sn.
Author(s): Fedin VP, Seo MS, Saysell DM, Dybtsev DN, Elsegood MRJ, Clegg W, Sykes AG
Publication type: Article
Publication status: Published
Journal: Journal of the Chemical Society: Dalton Transactions
Year: 2002
Issue: 2
Pages: 138-143
ISSN (print): 1472-7773
ISSN (electronic): 1364-5447
Publisher: Royal Society of Chemistry
URL: http://dx.doi.org/10.1039/b106522j
DOI: 10.1039/b106522j
Altmetrics provided by Altmetric
