Organolead compounds are of interest mainly as catalysts and organolead halides have proved to be very efficient materials for solar cells. Two organolead(IV) dimethylarsinates, namely catena-poly[[triphenyllead(IV)]-μ-chlorido-[triphenyllead(IV)]-μ-dimethylarsinato-κ2
O:O′], [Pb2(C6H5)6(C2H6AsO2)Cl]
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or [(Ph3Pb)2Cl(O2AsMe2)], (1), and poly[chlorido(μ3-dimethylarsinato-κ3
O:O,O′:O′)diphenyllead(IV)], [Pb(C6H5)2(C2H6AsO2)Cl]
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or [(Ph2ClPb)(O2AsMe2)], (2), together with the triphenyllead(IV) diphenylphosphinate catena-poly[[triphenyllead(IV)]-μ-diphenylphosphinato-κ2
O:O′], [Pb(C6H5)3(C12H10O2P)]
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or [(Ph3Pb)(O2PPh2)], (3), have been synthesized and characterized by single-crystal X-ray diffraction, IR spectroscopy and mass spectrometry. In (1), a chain structure was found with alternating chloride and Pb—O—As—O—Pb arsinate bridges between five-coordinate PbIV atoms. In (2), bidentate and chelate-like bonded dimethylarsinate ligands form double chains with heptacoordinated PbIV atoms. In (3), a pentacoordinated PbIV atom is connected by Pb—O—P—O—Pb phosphinate bridges to form a linear chain. Obviously, the steric demand of the phenyl ligands at PbIV reduces the possibility of interconnections via polydentate ligands to one dimension only. Thus, no metal–organic frameworks (MOF) are formed but instead various chain structures are observed.