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Chalcogen-capped ruthenium carbonyl clusters derived from diphosphazane mono- and dichalcogenides of the type $X_2P(E)N(R)PX_2$ and $X_2P(E)N(R)P(E)X_2$ $(E =S\hspace{2mm} or\hspace{2mm}Se)$

Venkatakrishnan, Thengarai S and Krishnamurthy, Setharampattu S and Nethaji, Munirathinam (2005) Chalcogen-capped ruthenium carbonyl clusters derived from diphosphazane mono- and dichalcogenides of the type $X_2P(E)N(R)PX_2$ and $X_2P(E)N(R)P(E)X_2$ $(E =S\hspace{2mm} or\hspace{2mm}Se)$. In: Journal of Organometallic Chemistry, 690 (17). 4001–4017.

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Abstract

Reactions of $Ru_3(CO)_1_2$ with diphosphazane monoselenides $Ph_2PN(R)P(Se)Ph_2$ $[R = (S)-*CHMePh(L^4),R =CHMe_2(L^5)]$ yield mainly the selenium bicapped tetraruthenium clusters $[R\mu_4(\mu_4-Se)_2(\mu-CO)(CO)_8\{\mu-P,P-Ph_2PN$(R)$PPh_2\}]$ (1,3). The selenium monocapped triruthenium cluster $[Ru_3(\mu_3-Se)(\mu_s_b-CO)(CO)_7$ $\{K^2-P,P-Ph_2PN((S)-\ast CHMePh)PPh_2\}]$ (2) is obtained only in the case of $L_4$. An analogous reaction of the diphosphazane monosulfide $(PhO)_2PN(Me)P(S)(OPh)_2$ $(L^6)$ that bears a strong $\pi$-acceptor phosphorus shows a different reactivity pattern to yield the triruthenium clusters, $[Ru_3(\mu_3-S)(\mu_3-CO)(CO)_7\{\mu-P,P-(PhO)_2PN(Me)$P$(OPh)_2\}]$ (9) (single sulfur transfer product) and $[Ru_3(\mu_3-S)_2(CO)_5\{k^2-P,P-(PhO)_2PN$(Me)P$(OPh)_2\}\{\mu-P,P-(PhO)_2PN$(Me)P$(OPh)_2\}]$(10) (double sulfur transfer product). The reactions of diphosphazane dichalcogenides with $Ru_3(CO)_{12}$ yield the chalcogen bicapped tetraruthenium clusters $[Ru_4(\mu_4-E)_2(\mu-CO)(CO)_8\{\mu-P,P-Ph_2PN$(R)$PPh_2\}]$ [R = (S)-\ast CHMePh, E = S (6); $R = CHMe_2$, E = S (7); $R = CHMe_2$, E = Se (3)]. Such a tetraruthenium cluster $[Ru_4(\mu_4-S)_2(\mu-CO)(CO)_8\{\mu-P,P-(PhO)_2PN(Me)$P$(OPh)_2\}]$ (11) is also obtained in small quantities during crystallization of cluster 9. The dynamic behavior of cluster 10 in solution is probed by NMR studies. The structural data for clusters 7, 9, 10 and 11 are compared and discussed.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Elsevier.
Keywords: Ruthenium;Cluster compounds;P ligands;Chalcogen clusters;Cluster dynamics;X-ray crystallography
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 13 Jul 2007
Last Modified: 19 Sep 2010 04:31
URI: http://eprints.iisc.ernet.in/id/eprint/8421

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