Oligomethylene-Bridged Dinuclear Triorganotin Triflates and Diphenylphosphinates. Ion Pairing in the Solid State and Electrolytic Dissociation in Solution of [Ph₂Sn(CH₂)_nSnPh₂X](O₃SCF₃) (X = OH, O₂PPh₂; n = 1−3)

Abstract

The condensation of [Ph2(OH)Sn(CH2) n Sn(OH)Ph2] (1−3; n = 1−3) with HO3SCF3 and HO2PPh2 provided [Ph2Sn(CH2) n SnPh2(OH)](O3SCF3) (4−6; n = 1−3) and [Ph2(O2PPh2)Sn(CH2) n Sn(O2PPh2)Ph2] (10−12; n = 1−3), respectively. The reaction of [Ph2Sn(CH2) n SnPh2(OH)](O3SCF3) (4−6; n = 1−3) with HO2PPh2 and NaO2PPh2 gave rise to the formation of [Ph2Sn(CH2) n SnPh2(O2PPh2)](O3SCF3) (7−9; n = 1−3) and [Ph2(OH)Sn(CH2) n Sn(O2PPh2)Ph2] (13−15; n = 1−3), respectively. In the solid state, compounds 4−9 comprise ion pairs of cationic cyclo-[Ph2SnCH2SnPh2(OH)]2 2+, cyclo-[Ph2Sn(CH2) n SnPh2(OH)]+ (n = 2, 3), and cyclo-[Ph2Sn(CH2) n SnPh2(O2PPh2)]+ (n = 1−3) and triflate anions. In MeCN, the eight-membered-ring system cyclo-[Ph2SnCH2SnPh2(OH)]2 2+ appears to be in equilibrium with the four-membered-ring system cyclo-[Ph2SnCH2SnPh2(OH)]+. In contrast, compounds 10−15 show no ionic character. Compounds 1−15 were characterized by multinuclear NMR spectroscopy in solution and in the solid state, IR spectroscopy, conductivity measurements, electrospray mass spectrometry, osmometric molecular weight determinations, and X-ray crystallography (4, 5, 7, and 12).

Hypercoordinated organotin triflates

“…The two MeCN molecules are associated with the hydroxy groups via hydrogen bonding. 35 In MeCN solution, compounds 6-8 undergo electrolytic dissociation into configurationally stable cyclic…”

“…n = 3) and triflate anions, indicated by 119 Sn NMR spectroscopy, conductivity measurements and electrospray mass spectrometry. 35 ) (9, n = 1; 10, n = 2; 11, n = 3), which were isolated as air-stable crystalline solids:…”

“…5 + cations (9a, n = 1; 10a, n = 2; 11a, n = 3) and triflate anions, indicated by 119 Sn and 31 P NMR spectroscopy, conductivity measurements and electrospray mass spectrometry. 35 The equimolar reaction of [Ph 2 Sn(CH 2 ) n SnPh 2 (OH)](O 3 SCF 3 ) (6, n = 1; 7, n = 2; 8, n = 3) with NaO 2 PPh 2 , the conjugated base of HO 2 PPh 2 , led to substitution of the triflate anion and produced [Ph 2 (OH)Sn(CH 2 ) n SnPh 2 (O 2 PPh 2 )] (12, Figure 5. X-ray structure of 9.…”

Linear alkaline earth metal phosphinate coordination polymers: synthesis and structural characterization

“…Orlandini and co-workers have expanded on this area with numerous reported structures involving diphosphinate anions (Costantino, Ienco et al, 2008;Bataille et al, 2008;Midollini et al, 2004Midollini et al, , 2006Ciattini et al, 2005;Cecconi et al, 2004;Berti et al, 2002). Their work also extended to the p-block with reports of lead(II) (Cecconi et al, 2003) and tin(II) (Beckmann et al, 2004(Beckmann et al, , 2005 compounds.…”

One- and two-dimensional CdIIcoordination polymers incorporating organophosphinate ligands

“…The structures of metal diphenylphosphinate compounds have been well studied for copper (Bino & Sassman, 1987), nickel (Annan et al, 1991), and manganese (Ruettinger et al, 1999;Du et al, 1991). Orlandini and coworkers have expanded the area to include studies on diphosphinates with transition metals (Costantino, Ienco et al, 2008;Bataille et al, 2008;Midollini & Orlandini, 2006;Ciattini et al, 2005;Midollini et al, 2004;Cecconi et al, 2004;Berti et al, 2002) and p-block metals (Cecconi et al, 2003;Beckman et al, 2004Beckman et al, , 2005. As part of our investigations in this area, we isolated one-and two-dimensional cadmium(II) coordination polymers incorporating diphenylphosphinate ligands.…”