PHOSPHORUS-31 NMR STUDIES ON BIS(DIPHENYLPHOSPHINO)-METHANE-BRIDGED PALLADIUM-SILVER HETERODINUCLEAR

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Bis (diphenylphosphino) methane (dppm)-bridged Pd-Ag complexes of nitrate,nitrite, acetate and formate have been prepared by treatment of trans- (NC)2Pd (dppm)2 with suitable silver salts respectively and characterized by elemental analysis, infrared spectroscopy,and by proton,carbon-13,phosphorus-31 nmr spectroscopies. Their 31P- {1H} nmr spectra have been analyzed by using the Bruker PANIC program for spectrum simulation to find the correct chemical shifts of the phosphorus atoms and P-P,P-Ag coupling constants of these complexes, each of which is a mixture of a pair of silver-107 and silver-109 isotopic isomers. A comparison of the 31P nmr data for trans-(NC)2Pd-(μ-dppm)2Ag(NO2) and for fo-oBs-(NC)2Pd(>-dppm)2Ag(NO3) shows that the additional oxygen atom in the nitrate complex withdraws p electron density, rather than s, from the silver moiety. Also a comparison of the 31P nmr data for trans- (NC)2Pd(μ-dppm)2Ag (OOCH) and for trans-(NC)2Pd(μ-dppm)2Ag(OOCCH3) shows that the methyl group in the acet Bis (diphenylphosphino) methane (dppm) -bridged Pd-Ag complexes of nitrate, nitrite, acetate and formate have been prepared by treatment of trans- (NC) 2Pd (dppm) 2 with suitable silver salts respectively characterized by elemental analysis, infrared spectroscopy, and by proton, carbon-13, phosphorus-31 nmr spectroscopies. Their 31P- {1H} nmr spectra have been analyzed by using the Bruker PANIC program for spectrum simulation to find the correct chemical shifts of the phosphorus atoms and PP, P -Ag coupling constants of these complexes, each of which is a mixture of a pair of silver-107 and silver-109 isotopic isomers. A comparison of the 31P nmr data for trans- (NC) 2Pd- (μ-dppm) 2Ag NO2) and for fo-oBs- (NC) 2Pd (> -dppm) 2Ag (NO3) shows that the additional oxygen atom in the nitrate complex withdraws p electron density, rather than s, from the silver moiety. 31P nmr data for trans- (NC) 2Pd (μ-dppm) 2Ag (OOCH) and for trans- (NC) 2Pd group in the acet
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