Synthesis and molecular structure of tin(IV) 1‐pyrrolecarbodithioates

Abstract

The 1-pyrrolecarbodithioate complexes of tin, PhSnC1-bipyramidal configuration. 1 attains approximately a cis-oc-(SZCNC4H4)z (1) and S~I ( S~C N C~H~)~ (2) have been synthesized tahedral geometry with two bidentate carbodithioate ligands and characterized by IR and NMR spectra ('H, I3C and "'Sn).with the C1 atom and the phenyl group in cis position. Com-6"' Sn suggests hexacoordination for 1 and an even higher plex 2 possesses two bidentate ligands while the other two are coordination number for 2. X-ray structure determinations of essentially anisobidentate leading to a structure between an these as well as of Me2Sn (SzCNC4H4)2 (3) have shown that 3 octahedraon and a dodecahedron. is one of the few known examples with a skew-trapezoidal Despite extensive synthetic and structural reports on metal dialkyldithiocarbamates".2' (R2NCS2),M those containing an aromatic R2N group received much less attention. Work by Bereman and on their transition metal complexes mark the beginning in that direction. Among the few known aromatic dithiolate complexes, those with the pyrrole ligand are especially interesting. And this ligand can be described with the canonical contribution A and B to its ground state. In this case a positive charge at the nitrogen atom would increase considerably the contribution of the dianionic electronic structure B. In addition, this ligand can act as bidentate, anisobidentate, or unidentate. c.Q S--o<--S c;-Q-S-From a recent study of the complete series of tin(1V) 1-pyrrolecarb~thioates[~~, R4 -,,Sn(SOCNC4H4),, an interesting trend has been witnessed for the bonding pattern of this asymmetrical sulfur-containing ligand. There is a change from an essentially unidentate to an anisobidentate behavior tending to become bidentate with concomitant increase in the Sn-0 interaction as n increases. This also reflects the stereoelectronic effect responsible for the molecular structure. It is not clear, however, wether in reference to a typical non-transition metal centre such as tin(1V) these evident features are the consequence of an oxygen-sulfur donor combination of the potentially bidentate ligand and/or the nature of the central tin atom. In this paper, we report on the synthesis of two new tin(1V) 1-pyrrolecarbodithioate complexes, PhSnC1(S2CNC4H4)2 (1) and Sn(S2CNC4H4)4 (2) as well as on their crystal and molecular structures and, in addition, also on the structure of Me2Sn (S2CNC4H4)2 (3)[61.

Synthesis and crystal structures of new complexes of di- and tribenzyltin 2-amino-1-cyclopentene-1-carbodithioates

“…Electronic and steric arguments have also been invoked to account for the distortion of similar structures from regular octahedral geometry. The geometry and bond lengths of the SnC 2 S 4 core are comparable with those observed for most other octahedral complexes, however, different from [ t Bu 2 Sn(IV)] 2+ ethylene bis-dtc and Ph 2 Sn(S 2 CNEt 2 ) 2 complexes[15,20,[22][23][24].…”

Tin dithiocarbamates: applications and structures

“…There are 10 structures with the general formula RSn(S 2 CNR 0 2 ) 2 Cl, [50 -59] and important tin atom parameters for these are listed in Table 2. The coordination geometry in each case is based on a distorted octahedron with the chloride and organo substituents being approximately cis-to each other; the prototype structure of PhSn(S 2 Cpyrrole) 2 Cl [57] is shown in Fig. 10.…”

Crystal structure of n-butyl-chlorido-bis[N-sec-butyl,N-n-propyl-carbamodithioato κ 2 S,S′]-tin(IV), C20H41ClN2S4Sn

“…In continuation of ongoing studies of the structural chemistry of molecules of the general formula RSn(S 2 CNR′R′′) 2 Cl, R, R′, R′′ = alkyl and/or aryl [2], the structure of the R = n-butyl, R′ = n-propyl and R′′ = secbutyl derivative, has been investigated. The structural motif adopted by the title molecule is common to all other molecules having this generic formula [2][3][4][5][6][7][8][9][10][11][12]. Thus, the Sn atom exists within a C, Cl, S4 donor set that describes a distorted octahedral geometry, being coordinated by n-butyl- …”