Lead(II) Siloxides.

Although PbII -siloxides have been known until now to decompose to oxoclusters, here [{ROF }PbOSi(SiMe3 )3 ] (ROF =fluoroalkoxide) and, most importantly, [Pb2 {OSi(SiMe3 )3 }{µ2 -OSi(SiMe3 )3 }3 ], are presented. The unusual bonding pattern in the latter thermally stable dinuclear complex was investigated by crystallographic and computational methods. Its stability is much higher than that of the simple, yet elusive "[Pb(OSiPh3 )2 ]", for which decomposition pathways towards [Pb4 (µ4 -O)(µ2 -OSiPh3 )6 ] have been clearly established.

Aminofluoroalkoxide amido and boryloxo lead(ii) complexes.

We report here on the utilisation of a readily available bidentate aminofluoroalkoxide in lead(ii) chemistry. Stable heteroleptic three-coordinate complexes can be produced in high yields, including a convenient amido synthetic precursor and a rare case of PbII-boryloxide.

Novel mono- and bimetallic organotin(iv) compounds as potential linkers for coordination polymers.

The reaction of [2-(O[double bond, length as m-dash]CH)C6H4]Me2SnCl (2), obtained by the hydrolysis of [2-{(CH2O)2CH}C6H4]Me2SnCl (1), with the appropriate diamine, in a 2 : 1 molar ratio, in the absence of a solvent or catalyst, resulted in the bimetallic species ClSnMe2[2-C6H4(4-CH[double bond, length as m-dash]N-1,1'-C6H4C6H4-4'-N[double bond, length as m-dash]CH)-2'-C6H4]Me2SnCl (4) and ClSnMe2[2-C6H4(CH[double bond, length as m-dash]NCH2CH2N[double bond, length as m-dash]CH)-2'-C6H4]Me2SnCl (5). The reaction of 2 and 5 with KSCN gave the corresponding isothiocyanates [2-(O[double bond, length as m-dash]CH)C6H4]Me2Sn(NCS) (3) and (SCN)SnMe2[2-C6H4(CH[double bond, length as m-dash]NCH2CH2N[double bond, length as m-dash]CH)-2'-C6H4]Me2Sn(NCS) (6). Treating 3 with H2NCH2CH2NH2 also resulted in the corresponding bimetallic compound 6. The reaction of 2 with sodium isonicotinate gave [2-(O[double bond, length as m-dash]CH)C6H4]Me2SnO(O)CC5H4N-4 (7) and the subsequent treatment with ZnTPP (TPP = tetraphenylporphyrinate) led to the isolation of the heterobimetallic complex [{2-(O[double bond, length as m-dash]CH)C6H4}Me2SnO(O)CC5H4N-4]ZnTPP (8). The compounds were characterized by multinuclear NMR spectroscopy and mass spectrometry in solution and IR spectroscopy in the solid state. The molecular structures for compounds 1-6 and 8 were established by single-crystal X-ray diffraction. For all compounds intramolecular O→Sn or Nimine→Sn coordination results in hypercoordinated species with a distorted trigonal bipyramidal (C,E)C2SnX core (E = O, Nimine; X = Cl, Nisothiocyanato, Oisonicotinato). In the heterobimetallic complex 8 the zinc atom has a distorted square pyramidal geometry with the Npyridyl atom at the apical position.

Stable lead(ii) boroxides.

The first examples of lead(ii) boroxides, [Pb(OB{CH(SiMe3)2}2)2] (1) and [{N^C}PbOB{CH(SiMe3)2}2] (5; N^C = 2-Me2NCH2C6H4), were prepared via simple protocols. These structurally characterised compounds are stable and, unlike lead(ii) alkoxides and siloxides, do not trigger uncontrolled formation of lead(ii) oxoclusters.