31~P NMR Studies on Quasi-Aromaticity of Mo_3S_3 Core and Structure of {Mo_3(μ_3-S)_3[μ-SOP(OEt)_2][S_2P(OEt)_2]_3(CH3CN)}*CH_3CN

1INTRoDUCTIoNDuringthisdecade,extensivestudieshavebeendoneontheclustercompoundswithMosS`coret1}.WehavedevelopedanewmethodtosynthesizeaseriesofMo,o.S'-.J' ,n=O,l,2,3,inaqueoussolution(2).BythereactionofaqueousclusterionswithHdtp,weobtainedtheircorrespondingcompoundswhichwerefirst-lysynthesizedbythespontaneousself-assemblymethod.Theseaqueousclusterionsandtheirderivativescoordinatedbyorganicligands,bothinaqueousphaseandnon-aqueoussolution,demonstratedreactiveactivitiestowardsmanytransitio…

31~P NMR Studies on Quasi-Aromaticity of Mo_3S_3 Core and Structure of {Mo_3(μ_3-S)_3[μ-SOP(OEt)_2][S_2P(OEt)_2]_3(CH3CN)}*CH_3CN

The title compound {Mo3 (μ3,-S) (μ-S)3 μ-SOP (OEt )2] S2P (OEt)2]3(CH3CN) }. CH3CN, C20H46,Mo3N2O9P4S11, Mr= 1222. 9, has been synthesized bythe reaction of Mo3 (μ3,-S) (μ-S)3]4+ with Hdtp (hydrogen diethyldithiophosphate)and its structures was dctermined by X-ray crystallography. The crystal data for the title compound: triclinic, P1, Z= 2, a= 13. 011 (8), b= 13. 411 (9), c= 14. 385 (5)A, a=76. 59(5), B=78. 09(5), Y=82. 20(3), V= 2382(2) A3, Dc= 1.705 g/cm3, μ (MoKa) = 1. 434 mm-1, F (000) = 1228. The structure was refined to R =0.080 for 5485 observed reflections. Quasi-aromaticity in the puckered-ring of Mo3S3was experimentally probed by 31p NMR spectroscopic measurements. The 31p chemicalshifts of ligand DTP's (diethyldithiophosphate) were modulated by the substituent effect of the adjacent bridging aromatic carboxylate through the long-distance super-conjugation via the trinuclear Mo cluster core.