Di- and tri-nuclear molybdenum-palladium complexes bearing strong $\pi$-acceptor "P-N-P" ligands, $MeN \lbrace P(OR)_2 \rbrace _2 (R = CH_2CF_3 \hspace{5mm}or\hspace{5mm}Ph)$

Ganesan, Mani and Krishnamurthy, Setharampattu S and Nethaji, Munirathinam (2005) Di- and tri-nuclear molybdenum-palladium complexes bearing strong $\pi$-acceptor "P-N-P" ligands, $MeN \lbrace P(OR)_2 \rbrace _2 (R = CH_2CF_3 \hspace{5mm}or\hspace{5mm}Ph)$. In: Journal of Organometallic Chemistry, 690 (4). pp. 1080-1091.

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Abstract

The dipalladium complexes, $[PdCl(\mu-MeN \lbrace P(OR)_2 \rbrace_2)]_2$ $\hspace{5mm}(R = CH_2CF_3, 1a; Ph, 1b)$ react with $[Mo_2(\eta^5-C_5H_5)_2(CO)_6]$ in boiling benzene to afford the molybdenum–palladium heterometallic complexes, $[(\eta^5-C_5H_5)(CO)Mo(\mu-MeN \lbrace P(OR)_2 \rbrace _2)_2PdCl]$ $(R = CH_2CF_3, 3a; Ph, 3b)$, $[(\eta^5-C_5H_5)Mo(\mu_3-CO)_2$ $(\mu-MeN \lbrace P(OR)_2 \rbrace_2)_2Pd_2Cl]$, $(R = CH_2CF_3, 5a; Ph, 5b)$, $[(\eta^5-C_5H_5)(Cl)Mo(\mu_2-CO)(\mu_2-Cl)$ $(\mu-MeN \lbrace P(OR)_2 \rbrace_2)PdCl]$, $(R = CH_2CF_3, 6a; Ph, 6b)$ and also the mononuclear complex $[Mo(CO)Cl(\eta^5-C_5H_5)(\kappa^2-MeN \lbrace P(OR)_2\rbrace_2)]$, (R = Ph, 4b). These complexes have been separated by column chromatography and are characterised by elemental analysis, IR, $^1H$, $^3^1P\lbrace^1H\rbrace$ NMR data. The structures of 1a, 3a, 4b, 5b and 6a have been confirmed by single crystal X-ray diffraction. The CO ligands in 5b and 6a adopt a semi-bridging mode of bonding; the Mo–CO distances $(1.95-1.97 \AA)$ are shorter than the Pd–CO distances $(2.40-2.48 \AA)$. The Pd–Mo distances fall in the range, $2.63-2.86 \AA$ . The reaction of $[Mo_2(\eta^5-C_5H_5)_2(CO)_6]$ with $MeN \lbrace P(OPh)_2 \rbrace_2$ in toluene gives $[Mo_2(CO)_4(\eta^5-C_5H_5)_2$ $(\kappa^1-MeN \lbraceP(OPh)_2 \rbrace_2)_2]$ (2) in which the diphosphazane acts as a monodentate ligand.

Item Type:	Journal Article
Publication:	Journal of Organometallic Chemistry
Publisher:	Elsevier
Additional Information:	The Copyright belongs to Elsevier.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	17 Mar 2006
Last Modified:	19 Sep 2010 04:24
URI:	http://eprints.iisc.ac.in/id/eprint/5807

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