Inorganic-organic hybrids of the p,p'-diphenylmethylenediphosphinate, pcp2-. Synthesis, characterization, and XRPD structures of [Sn(pcp)] and [Cu(pcp)].

Two new inorganic-organic polymeric hybrids [Sn(pcp)] and [Cu(pcp)], pcp=CH2(PhPO2)2(2-), have been synthesized and structurally characterized. The tin derivative has been obtained by reaction of the p,p'-diphenylmethylenediphosphinic acid (H2pcp) in water with SnCl2.2H2O, while the copper derivative has been synthesized through a hydrothermal reaction from the same H2pcp acid and Cu(O2CMe)2.H2O. The structures of these compounds have been solved "ab initio" by X-ray powder diffraction (XRPD) data. [Sn(pcp)] has a ladder-like polymeric structure, with tin(II) centers bridged by diphenylmethylenediphosphinate ligands, and alternating six- and eight-membered rings. The hemilectic coordination around the metal shows the tin(II) lone pair to be operative, resulting in significant interaction mainly with a C-C bond of one phenyl ring. The [Cu(pcp)] complex displays a polymeric columnar structure formed by two intersecting sinusoidal ribbons of copper(II) ions bridged by the bifunctional phosphinate ligands. The intersections of the ribbons are made of dimeric units of pentacoordinated copper ions. Crystal data for [Sn(pcp)]: monoclinic, space group P2(1)/c, a=11.2851(1), b=15.4495(6), c=8.6830(1) A, beta=107.546(1) degrees, V=1443.44(9) A, Z=4. Crystal data for [Cu(pcp)]: triclinic, space group P, a=10.7126(4), b=13.0719(4), c=4.9272(3) A, alpha=92.067(5), beta=95.902(7), gamma=87.847(4) degrees, V=685.47(7), Z=2. The tin compound has been characterized by 119Sn MAS NMR (magic-angle spinning NMR), revealing asymmetry in the valence electron cloud about tin. Low-temperature magnetic measurements of the copper compound have indicated the presence of weak antiferromagnetic interactions below 50 K.

The utility of hypercoordination and secondary bonding for the synthesis of a binary organoelement oxo cluster.

A strategy for the preparation of the otherwise difficult to obtain binary organometallic oxides containing two heavy main group elements is described and exemplified by the synthesis of [(p-MeOC6H4)2Te(OSnt-Bu2OH)2]2.

Solvent-controlled assembling by hydrogen bridges and halogen-halogen interactions of novel organotin oxo clusters.

The crystal structure of the novel methylene-bridged tetraorganodistannoxane ([Ph(HO)SnCH2Sn(I)Ph]O)4 (1) depends on the solvent it is crystallised from and is controlled by hydrogen bridges and interhalogen interactions.

Molecular Dynamics within Diorganotin Systems: Solution and Solid State Studies of New Mixed Distannoxane Dimers [(t)Bu(2)(Cl)SnOSn(Cl)R(2)](2).

Di-tert-butyltin oxide, ((t)Bu(2)SnO)(3), reacts with R(2)SnCl(2) to give mixed distannoxanes [(t)Bu(2)(Cl)SnOSn(Cl)R(2)](2) (1, R = Me; 2, R = Et; 3, R = (i)Pr; 4, (n)Bu) whereas di-tert-butyltin hydroxide chloride, [(t)Bu(2)Sn(OH)Cl](2), reacts with [(n)Bu(2)SnO](n) to give the chlorohydroxydistannoxane [(t)Bu(2)(OH)SnOSn(Cl)(n)Bu(2)](2), 5; the dimeric nature of these tetraorganodistannoxanes was confirmed by crystal structure determinations of 1 and 4. Although stable in the solid state, compounds 1-4 rearrange to give a number of distannoxanes in solution. Addition of R(2)SnCl(2) (R = Me, (i)Pr, (n)Bu) to solutions of 1, 3, and 4, respectively, causes displacement of (t)Bu(2)SnCl(2) with concomitant formation of [((t)Bu(2)SnCl(2))(R(2)SnO)(2)(R(2)SnCl(2))] and [(R(2)SnCl(2))(R(2)SnO)(2)(R(2)SnCl(2))]. Thus 1-4 can be regarded as (R(2)SnO)(2) units which are stabilized by two (t)Bu(2)SnCl(2) molecules. NMR data indicate that reaction between ((t)Bu(2)SnO)(3) and (t)Bu(2)SnCl(2) gives rise to an equilibrium involving linear [(t)Bu(2)Sn(Cl)OSn(Cl)(t)Bu(2)] and the novel three-quarter ladder compound [(t)Bu(2)SnCl(2)][(t)Bu(2)SnO](2). Formation of trinuclear tin species is also evident from electrospray mass spectrometric studies.