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Formation (and properties) of palladium derivatives of [Mo(3)Q(4)(H2O)(9)](4+): absence of similar derivatives of [W(3)Q(4)(H2O)9](4+) (Q = S, Se)

Lookup NU author(s): Mi-Sook Seo, Dr Mark Elsegood, Emeritus Professor Bill Clegg, Emeritus Prof Alfred Sykes


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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.

Publication metadata

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


DOI: 10.1039/b106522j


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