648930-61-4Relevant academic research and scientific papers
New Hypercoordinating Organostannanes for the Modular Functionalization of Mono- and Polystannanes: Synthetic and Computational Studies**
Choi, Jung-Won,Foucher, Daniel A.,Gossage, Robert A.,Lough, Alan J.,Pau, Jeffrey,Ranne, Mokhamed,Silverthorne, Kaitlyn,Wylie, R. Stephen
, (2022/02/16)
A series of potentially hypercoordinate tin compounds derived from a substitutionally labile tosyl stannane (5) was produced to gain access to a library of propyloxybiphenyl (11), propylmethoxy (12, 14, 18, 22) or propylthioester (13, 15, 19, 23) stannanes for structure/property/polymerization investigations. Structural characterizations by single crystal X-ray diffraction of 12, 14, 18 and 19 were also undertaken. The relative energies of hypercoordinate conformers for the propylmethoxystannanes 12, 14, 18, and 22 were determined with DFT methods and the fractional abundance of conformers in the gas and solution (CHCl3) phase were estimated. Relativistic DFT calculations of 119Sn NMR chemical shifts were carried out for a series of non-hypercoordinate reference compounds and the conformers, allowing the estimation of Boltzmann-averaged chemical shifts of the hypercoordinate propylmethoxystannanes. A semi-crystalline homopolymer (25) was isolated from the dehydropolymerization of 22 using Wilkinson's catalyst. Conversion of the liable tosylated polystannane (24) to a new partially substituted polystannane (28) via nucleophile displacement reactions was achieved.
Reduction of C,O-chelated organotin(IV) dichlorides and dihydrides leading to protected polystannanes
Khan, Aman,Komejan, Sarah,Patel, Aagam,Lombardi, Christopher,Lough, Alan J.,Foucher, Daniel A.
, p. 180 - 191 (2015/02/19)
A series of aryloxy organotin compounds Ph3Sn(CH2)3OC6H4R (5: R = H; 6: R = Ph; 7: R = OCH3, 8: R = CF3), Ph2ClSn(CH2)3OC6H4R (9: R = H; 10: R = Ph) and PhCl2Sn(CH2)3OC6H4R (12: R = H; 13: R = Ph) have been synthesized and characterised by NMR (1H, 13C, 119Sn) spectroscopy. X-ray structure determinations of 9, 10, 12 and 13 reveal a distorted trigonal bipyramidal geometry at Sn with Cl trans to the datively bonded O whereas 8 possesses tetrahedral geometry and a Sn? dative interaction is absent. Triorganotin hydrides Ph2HSn(CH2)3OC6H4R (14: RH; 15: RPh) and diorganotin dihydrides PhH2Sn(CH2)3OC6H4R (16: RH; 17: RPh) were prepared by reduction of the corresponding dihalides with LiAlH4. Catalytic dehydrocoupling of dihydrides 16 or 17 with a late transition metal catalyst afforded asymmetrical hypercoordinated polystannanes [PhSn(CH2)3OC6H4R]n (18: RH; 19: RPh) with relatively high molecular weights (Mw 1.3 104 e 2.5 105 Da) and narrow polydispersities (PDI's 1.3e3.3). NMR and UVeVis spectroscopy studies indicate that the new polymers display dramatically improved light stability, but remain sensitive to moisture.
Organotin compounds bearing mesogenic sidechains: Synthesis, X-ray structures and polymerisation chemistry
Deacon,Devylder,Hill,Mahon,Molloy,Price
, p. 46 - 56 (2008/10/08)
Organotin compounds R3Sn(CH2)n+2OC 6H4C6H4Y (R3=Ph 3, Ph2Bu; Y=H, CN; n =1-3) and RX2Sn (CH2)n+2OC6H4C6 H4Y (R=Ph, Bu; Y=H, CN; X=Br, I; n=1-3) have been synthesised and characterised by 1H-, 13C-, 119 Sn-NMR and M?ssbauer spectroscopies. X-ray crystallography reveals tetrahedral geometries for Ph3Sn(CH2)4 OC6H4C6H5 and Ph3 Sn(CH2)3OC6H4C6 H4CN, a six-coordinated, bromine-bridged dimeric structure for PhBr2Sn(CH2)3OC6 H4C6H5 containing a mer-Br3 C2OSn coordination sphere about tin and a five-coordinated monomeric structure for PhBr2Sn(CH2)3 OC6H4C6H4CN. In all cases there is strong alignment of mesogenic groups in the solid-state but only PhBr2Sn(CH2)3OC6 H4C6H4CN shows any indication of liquid-crystal behaviour. Wurtz polymerisation of RBr2 Sn(CH2)5OC6H4C6 H5 (R=Ph, Bu), both of which contain non-chelating ether functions, generated polystannanes (RR′Sn)n with Mn 2.3×105; Mw 3.0× 105; Mw/Mn 1.30 and Mn 1.3×105; Mw 2.5×105; Mw/Mn 1.96, respectively, while no polymer was obtained from chelated PhBr2Sn(CH2)3 OC6H4C6H5
