Luc J.-M. Pierssens

Synthesis and X-ray molecular structures of the silver(I) amides [{Ag[µ-N(SiMe3)2]}4] and [{Ag[µ-NCMe2(CH2)3CMe2]}4]

The thermally stable silver(I) amides [{Ag(µ-NR2)}4](R = SiMe3) 1 and [{Ag(µ-NR′2)}4][NR′2= [graphic omitted]Me2] 2, prepared from AgNCO and Sn(NR2)2 or Sn(NR′2)2, or for 1 also from M(NR2)2(M = Pb or Yb) or [{Sn(µ-F)NR2}2], are centrosymmetric, tetranuclear clusters comprising a square of Ag atoms [mean Ag⋯Ag 3.001(2)A for 1 and 2.995(2)A for 2] linked by singly bridging amido groups [mean Ag–N 2.148(5)A for 1 and ranging from 2.126(7) to 2.184(7)A for 2], the (AgN)4 macrocycle being planar for 1 but puckered for 2, and the N–Ag–N′ and Ag–N–Ag′ arrangements being essentially linear and rectangular, respectively.

Synthesis and structural characterisation of bis(trimethylsilyl)amidotin(II) triflate [{Sn(NR2)(μ-η2-∞ (R=SiMe3, −OTf=−OSO2CF3)

Abstract The amidotin(II) triflate [{Sn(NR 2 ){μ-η 2 - OTf)} 2 ] ∞ ( 1 ) has been prepared in high yield by two methods: from Sn(NR 2 ) 2 +HOTf, or from [Sn(NR 2 )(μ-Cl)] 2 +2AgOTf (R=SiMe 3 , − OTf= − OSO 2 CF 3 ). The triflate ligand in the crystalline compound 1 binds to two tin atoms in an O , O ′-bridging fashion (av. SnO 2.395(4) A) and uses its third oxygen atom to bind more loosely to a tin atom of a neighbouring dinuclear tin unit [av. SnO″ 2.832(4) A]. Multinuclear [ 1 H-, 13 C-, 19 F- and 119 Sn- ( δ −78.0 in PhMeC 6 D 6 at 298 K)] NMR and 119 Sn Mossbauer (I.S. 3.37, Q.S. 3.75 mm s −1 ) spectral data are reported.

Synthesis and characterisation of twelve SnIV diaryls and formation of a SnIII triaryl

Ten new crystalline compounds of formula (i) [{Sn(Ar(N2))(2)(micro-E)}(2)] [E = O (), S (), Se (), Te ()], (ii) [Sn(Ar(N2))(2)(ER)(2)] [ER = SCH(2)Ph (), SePh (), TePh ()], (iii) [Sn(Ar(N2))(2)(Br)R] [R = CH(SiMe(3))(2) (), Bu(t) ()] and (iv) [Sn(Ar(N2))(2){CH(SiMe(3))(2)}][BPh(4)] [Ar(N2) = C(6)H(3)(NMe(2))(2)-2,6 ()] have been prepared and identified by microanalysis, EI-mass spectrometry and multinuclear NMR spectroscopy, and for , , , and by single crystal X-ray diffraction. Whereas in the solid state, each of the latter five has only one of its two NMe(2) substituents of each [Ar(N2)](-) ligand close to the tin atom (<3.1 A), in solution at ambient temperature the NMe(2) groups are characterised by a single (1)H and (13)C signal. The known compounds [Sn(Ar(N2))(2)(NCE)(2)] [E = O (), S ()] were synthesised by a new route: the redox reaction between [Sn(Ar(N2))(2)] () and 2AgNCE. Irradiation of a toluene solution of at 298 K afforded a persistent radical assigned as [ Sn(Ar(N2))(3)] ().

The novel, chelating C, N-bidentate 2,6-bis(dimethylamino)phenylligand (R-), showing ambidentate N,N′-character inM(R)2 (M = Ge, Sn, Pb) and Sn(R)X [X =N(SiMe3)2, CH(SiMe3)2,Cl]

Treatment of MCl 2 or [Sn(µ-Cl){N(SiMe 3 ) 2 }] 2 with [Li(µ-R)] 3 [R = C 6 H 3 (NMe 2 ) 2 -2,6] under mild conditions and in appropriate stoichiometry affords MR 2 (M = Ge 1, Sn 2, Pb 3) or Sn(R)X [X = N(SiMe 3 ) 2 4, Cl 6], while 4 or 6 with LiCH(SiMe 3 ) 2 give SnR[CH(SiMe 3 ) 2 ] 5; compounds 1–6 are characterised by their multinuclear NMR and MS spectra and 1–3 by X-ray crystal structures.