Two Successive Steps of Hypercoordination at Tin: The Gas-Phase and Solid-State Structures of (N,N-Dimethylaminoxy)trimethylstannane

Abstract

Me3SnONMe2 has been prepared from trimethyltin chloride and O-lithio-N,N-dimethylhydroxylamine and characterized by IR and NMR spectroscopy, mass spectrometry, and elemental analysis. Its gas-phase molecular structure has been determined by electron diffraction augmented by restraints taken from ab initio calculations at the MP2/DZ(P) level of theory. A secondary interaction (Sn···N, 2.731(14) Å) between the tin and nitrogen atoms has been detected and makes Me3SnONMe2 the first partially hypercoordinate tin compound studied in the gas phase. A solid-state structure of Me3SnONMe2 has been determined by X-ray diffraction of an in situ grown single crystal. In the crystal lattice the coordination sphere of tin is further enlarged by a weak intermolecular Sn···O contact (2.998(10) Å) and a 4+2 coordination geometry is achieved, which can be deduced from that of a distorted trigonal bipyramid with one of the axial substituents replaced by the two weak contacts. Important geometry parameter values are as follows (gas/solid): Sn−O 2.006(3)/2.063(6) Å, O−N 1.468(6)/1.440(9) Å, Sn−C(in plane) 2.148(4)/2.163(14) Å, Sn−C(out of plane) 2.146(3)/2.062(9) and 2.185(10) Å, Sn−O−N 102.5(8)/101.5(4)°, O−Sn−C(in plane) 99.6(10)/99.7(4)°, O−Sn−C(out of plane) 108.1(6)/119.6(4)° and 116.6(4)°.

Strong Intramolecular Secondary Si⋅⋅⋅N Bonds in Trifluorosilylhydrazines

“…This allowed us to compare F 3 SiN(SnMe 3 )NMe 2 (4) with (Me 3 Sn)N(SnMe 3 )NMe 2 (5), and thereby, to study the effects of exchanging the electrophilic F 3 Si group for the less Lewis acidic Me 3 Sn group, which has been shown to act as a weak acceptor in the geminal system Me 3 SnONMe 2 . [20] In compound 5, the NMe 2 group leans slightly towards the Sn2 atom; this leads to one Sn-N-N angle being smaller and one larger (Sn2-N-N 109.5(4)8, Sn1-N-N 125.2(4)8). The Sn1Me 3 group has an almost tetrahedral coordination geometry around tin, with all the N-Sn-C angles lying between 107.7(3) and 108.1(3)8.…”

Inherent Stability Limits of Intramolecular Boron Nitrogen Lewis Acid–Base Pairs

“…According to Bader’s quantum theory of atoms in molecules (QTAIM),9 its charge density topology is that of an open‐chain system, as no bond critical point for the NB interaction is found and accordingly no ring critical point. In this sense the system behaves similarly to compounds with SiON (X 3 Si‐O‐NR 2 ),10 SnON11 and SiNN units (X 3 Si‐N(R′)‐NR 2 ,12 which show short SiN/SnN distances and small Si‐O‐N, Sn‐O‐N and Si‐N‐N angles, respectively. We have studied such compounds intensely in the course of our investigations on the α effect in silicon chemistry 13.…”

Use of C,N-chelated triorganotin(IV) fluoride for fluorination of organic compounds, coordination compounds, phosphines, silanes and stannanes

“…This method is very effi cient if fi ve-or six-membered metallacycles are formed, which stabilize metal-carbon bonds and yield to these complexes interesting physicochemical properties. The most often studied organometallic compounds (Holmes , 1990 ;Jastrzebski , 1991a;Jastrzebski et al, 1991b ;Jastrzebski and van Koten , 1993 ;Chuit et al , 1996 ;Buntine et al , 1999 ;Mitzel et al , 1999 ;Albrecht and van Koten , 2001 ;Akiba , 2002 ;Morales -Morales and Jensen, 2007 ) Organometallic compounds containing C, Y-or Y, C,Ychelating ligands. Nov á k et al, 2005Nov á k et al, , 2006Nov á k et al, , 2007Chandra et al , 2006 ;Š vec et al, 2007 ).…”