Insertion of SnCl₂ into Pt–Cl bonds: synthesis and characterization of four- and five-coordinate trichlorostannylplatinum(II) complexes

QR‐SCMEH‐MO calculations on the complex [Pt (SnCl3)5]3−: Electronic structure, UV–visible spectrum, magnetic properties, and bond energy

“…The X‐ray structural data1 show equatorial PtSn bond distances of 4.82au at 120° ± 0.03 angles and axial distances of 4.80 au with 90° axial/equatorial angles. The geometry is a trigonal bipyramid with D 3h symmetry, although evidence indicates it not to be totally rigid D 3h symmetry.…”

“…The QR‐SCMEH‐MO method employed in this calculation, incorporated quasi‐relativistic atomic functions were used for Pt and Sn, but nonrelativistic functions for Cl. Inter atomic distances were taken directly from the X‐ray structural data 1. Unfortunately, much of this calculation had to be made without the aid of the complete computer routine normally employed.…”

“…Ever since the preparation and X‐ray structural characterization of (HNEt 3 ) 3 [Pt (SnCl 3 ) 5 ]1 the coordination number of 5 for Pt is unique to SnX (X = Cl − , Br − ) ligands, as in all other cases Pt invariably has coordination numbers 4 (planar) and 6 (octahedral), excepting carbonyl clusters. The Pt complexes with tri‐halostannane ligands have been subjected to some detailed experimental investigations,2 and considerable attention has been directed to PtSnCl 3 bonded systems because of their significance in structural chemistry and catalysis 3.…”

Rational Syntheses and Serendipity: Complexes [LSnPtCl2(SMe2)]2, [{LSnPtCl(SMe2)}2SnCl2], [(LSn)3(PtCl2)(PtClSnCl){LSn(Cl)OH}], and [O(SnCl)2(SnL)2] with L=MeN(CH2CMe2O)2

“…Molecular structure of 6·3CH 2 Cl 2 (ORTEP presentation at 30 % probability of the depicted atomsa nd atom numbering scheme).T he solvent molecules werer emoved by the squeeze routine of the program Platon. [21] Selectedi nteratomic distances []: Pt(1)ÀSn (1) cule (1)i nteracts with the MeN(CH 2 CMe 2 O) 2 Sn(Cl)OH moiety by intermolecular O!Sn coordination at distances of 2.063 (7) (Sn(5)ÀO(41))a nd 2.180(7) (Sn(4)ÀO(50)) and complexes the Pt(1) center (Pt(1)ÀSn(4): 2.5211 (8) ). The central tetra-coordinated Sn(1) atom symmetrically bridgest he platinum centers at Pt(1)ÀSn(1) and Pt(2)ÀSn(1) distances of 2.5290(8) and 2.5274(8) ,r espectively,a nd adopts as trongly distorted tetrahedral environment.…”

“…[4] In this context, we extendedt he chemistry of 1 to reactions with platinum(II) chloride, PtCl 2 ,a nd its more soluble complex dichloridobis(di-methylsulfide)platinum(II), PtCl 2 (SMe) 2 ,i no rder to prove whetheri tb ehaves as at wo-electron s-donor ligando ri nserts into PtÀCl bonds. It is well known from literature that divalent tin compounds are able to insert into PtÀCl bonds but previous research was limited to tin(II)chloride [5][6][7][8][9][10] and stannylenes of the type SnR 2 (R = CH(SiMe 3 ) 2 ,N {CH(SiMe 3 ) 2 } 2 ,N (SiMe 3 ) 2 ), [11][12][13][14] and Me 2 Si(N-2,6-iPr2 C 6 H 3 )2 Sn . [15] In analogy, dichloridobis(dimethylsulfide)platinum(II) reacts with two molar equivalents of tin(II)c hloride dihydrate to give tris[chloridotris(dimethylsulfide)platinum(II)]pentakis(trichloridostannyl)platinate(II), [PtCl(SMe 2 ) 3 ] 3 [Pt(SnCl 3 ) 5 ].…”