Synthesis and Reactivity of Organotin Compounds Containing the C,P-Chelating o-Carboranylphosphino Ligand [o-C₂B₁₀H₁₀PPh₂-C,P](Cab^C,P). X-ray Structures of (Cab^C,CH₂P)SnMe₂Br, [(Cab^C,P)SnMe₂]₂Pd, and [(Cab^C,P)SnMe₂]Pd(PEt₃)Cl

Abstract

The triorganotin halides (Cab C,P )SnMe 2 X (2a, X ) Cl; 2b, X ) Br) and a tetraorganotin compound (Cab C,P )SnMe 3 (7), containing the o-carboranylphosphino ligand (Cab C,P ), have been prepared by the reaction of LiCab C,P (1) with Me 2 SnX 2 and Me 3 SnCl, respectively. 1 H, 13 C, 31 P, and 119 Sn NMR spectroscopy indicate that the tin centers in 2a and 2b are pentacoordinate as a result of intramolecular Sn-P coordination, whereas the tin center in 7 is tetracoordinate. The substitution reactions of 2a using NaI, NaN 3 , NaCpFe(CO) 2 , and NaB(CN)H 3 afforded the substituted products (Cab C,P )SnMe 2 X (3, X ) I; 4, X ) N 3 ; 5, X ) CpFe(CO) 2 ; 6, X ) H). The Wurtz-type coupling reaction of 2a with sodium afforded the distannane. The reaction of the distannane 10 with Pd 2 (dba) 3 ‚CHCl 3 afforded the bis(stannyl)palladium complex 11. When compounds 2a and 2b were employed in the reaction with Pd 2 (dba) 3 , the halo-bridged metal complexes 12a and 12b were isolated. The crystal structures of 9b, 11, and 13 were determined by X-ray structural studies. As a result of the Sn-P interaction, the tin atom in 9b exhibits a distorted trigonal-bipyramidal configuration.Supporting Information Available: Tables listing crystallographic information, atomic coordinates and Beq values, anistropic thermal parameters, and intramolecular bond distances, angles, and torsion angles for 9b, 11 and 13. This material is available free of charge via the Internet at http://pubs.acs.org. OM0007872

Preparation, Structure, and Ethylene (Co)Polymerization Behavior of Group IV Metal Complexes with an [OSSO]‐Carborane Ligand

“…The local atomic environment and charge state of the metal center in complexes 2 c and 2 d were further confirmed by X-ray absorption spectroscopy, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) analyses (Figures 4 and 5). (14), S(1)-Ti(1)-S(2) 77.45(4), Cl(1)-Ti(1)-Cl(2) 106.70 (7).…”

“…[4] In material science or chemical research, the rational design of new o-carborane-derived materials has attracted much attention. [5] Some reports on unusually stable C,N-, [6] C,P-, [7] N,S-, [8] N,P-, [9] and S,S-chelating [10] o-carboranyl metal complexes seem to imply that the rigid chelate conformation and the ortho-carboranyl ligand backbone might be ideal for the stabilization of possible metal intermediates in organometallic reactions. However, to the best of our knowledge, there are few reports on using carborane ligands to synthesize olefin polymerization catalysts.…”

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

“…Kang et al investigated [170] reactions of triorganotin halides containing intramolecular Sn-P coordination. One such reaction was chloro substitution on tin in 1-PPh 2 -2-SnClMe 2 -1,2-C 2 B 10 H 10 by the Fp moiety.…”

Noncovalent Tagging Proteins with Paramagnetic Lanthanide Complexes for Protein Study

“…In the past few years, the interest in transition‐metal complexes with ligands containing dissimilar donor atoms has increased, primarily for their application in important homogeneous catalytic processes 1–8. Recent reports on unusually stable C,N‐,9 C,P‐,10 N,S‐,11 N,P‐,12 and S,S′‐13chelating o ‐carboranyl metal complexes seem to imply that the rigid chelate conformation and the ortho ‐carboranyl ligand backbone might be ideal for the stabilization of possible metal intermediates in organometallic reactions. Therefore, the design of such a ligand system containing one functional group strongly bound to a transition metal center and another one coordinatively labile has been of considerable interest 14–18…”