Synthesis and Mössbauer spectra of six-co-ordinate tin–metal compounds: quotient of the partial quadrupole splittings of the six- and four-co-ordinate species
- 1 January 1976
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 5,p. 467-473
- https://doi.org/10.1039/dt9760000467
Abstract
Nine new six-co-ordinate tin(IV) compounds have been prepared of the type [M(SnCl3L)][M = Mn(CO)5, Mn(CO)4(PPh3), Fe(cp)(CO)2; L = phen or bipy], [M(SnXL′2)](X = Cl or Ph; L′= quin or pd), and [M{SnPhCl2(phen)}]. Structures for these and other similar compounds have been assigned using carbonyl i.r. stretching frequencies and 119Sn Mössbauer quadrupole splittings. Partial quadrupole splittings for six-co-ordinate species, (p.q.s.)L oct, have been calculated from these quadrupole splittings. There is an excellent linear corrleation (R 0.991) between the (p.q.s.)L oct values and previously calculated (p.q.s.)L tet values: (p.q.s.)L oct= 0.73(p.q.s)L tet–0.01. The gradient of 0.73 is compared with that (0.67) calculated previously from molecular-orbital arguments. The relative bonding characteristics for the M groups in six-co-ordination are the same as those evaluated for M groups in four-co-ordinate compounds. Thus, the order of p-donor strength in six-co-ordination is Mo(cp)(CO)3 < Mn(CO)5 < Mn(CO)4(PPh3)≈ Fe(cp)(CO)2 < Ph < Me, while the M–Sn bonds have substantially higher Sn 5s character than Me or Ph–Sn bonds.Keywords
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