The O,C,O-Coordinating Pincer-Type Ligand {2,6-[P(O)(OEt)₂]₂-4-t-Bu-C₆H₂}^- in Organotin Chemistry. Halide Exchange, Cyclization, and Novel Coordination Mode

Abstract

Reactions in solution of the hypercoordinated organotin chlorides {2,6-[P(O)(OEt) 2 ] 2 -4-t-Bu-C 6 H 2 }SnCl 2 X (X ) Ph, Cl) with fluoride ions have been studied using temperaturedependent 119 Sn and 31 P NMR spectroscopy and electrospray mass spectrometry. The syntheses and molecular structures of the novel intramolecularly coordinated diorganotin difluoride {2,6- 3), and the monoorganotin difluoride hydroxide {{2,6-[P(O)(OEt) 2 ] 2 -4-t-Bu-C 6 H 2 }SnF 2 OH} 2 (6) are reported. In the crystal lattice, compound 1 forms an adduct composed of two tin moieties and a water molecule which are linked via F‚‚‚H-O-H‚‚‚F hydrogen bridges. The intramolecularly coordinated benzoxaphosphastannole derivative 3 is formed by intramolecular cyclization of {2,6-[P(O)(OEt) 2 ] 2 -4-t-Bu-C 6 H 2 }SnCl 2 Ph with elimination of ethyl chloride and dimerization. The organotin difluoride hydroxide derivative 6 is a dimer in the solid state as a result of intermolecular hydroxide bridges. Also present are intramolecular Sn-O-H‚‚‚OdP hydrogen bonds. The configuration at tin is best described as a monocapped octahedron.

The First [4+2]-Coordinated Tetraorganolead Compound: Synthesis, Structure and Conversion into a Triorganolead Cation, a Benzoxaphosphaplumbole, and Diorganolead Dihalides

“…The molecular structure of 2 is shown in Figure 1, selected geo- (1) 98.51 (9) 113.1(4) P(2)-O(2)-Pb (1) 98.02(9) P(2)-O(2Ј)-Pb (1) 117.9(4) Pb(2)-O(2)-P (2) 145.5(4) O(2)-Pb(2)-Cl (1) 178.9(2) C(61)-Pb(2)-C (41) 108.2(4) C(51)-Pb(2)-C (41) 127.9(4)…”

“…ECE-coordinating pincer-type ligands of the general type [2,6-(ECH 2 ) 2 C 6 H 3 ] Ϫ containing mainly E ϭ nitrogen [1Ϫ20], phosphorus [1, 20Ϫ31], and sulfur [1, 32Ϫ34] donors have received great interest as result of their potential (i) to stabilize organometallic compounds of both main group and transition metals with the metal atoms having unusual coordination numbers and (ii) to tune the reactiv- [37,42] and tetraorganotin [35] compounds, of triorganosilicon [43] and triorganotin [38,41,44] cations, of benzoxasilaphospholes [43] and benzoxaphosphastannoles [38,41], and of heteroleptic tin(II) compounds [40].…”

Solid‐State Structure and Behaviour in Solution of Hypervalent Organotin(IV) Derivatives Containing 2‐(Me2NCH2)C6H4 Moieties

“…Diorganotin(IV) difluorides [Me 2 N-(CH 2 ) 3 ] 2 SnF 2 ·2H 2 O and {2,6-[(EtO) 2 P(O)] 2 -4-tBu-C 6 H 2 }-PhSnF 2 are straightforward examples for such behaviour. [12,45] In the case of compound 2, the presence of only one dimethylaminomethyl group with a potential for intramolecular coordination is not enough to provide a monomeric species; an octahedral coordination of the tin atom is achieved by intermolecular FǞSn coordination to give a polymer. Its very low solubility prevents detailed NMR spectroscopic studies in solution.…”

The UV‐Light Initiated Reaction of Organosilanes with Tungsten Hexacarbonyl: Formation of an Organosilylene Complex and Organosilylium Salts

“…For some years we have been interested in the application of phosphorus-containing O,C,O-coordinating pincer-type ligands to the synthesis of, among others [33][34][35][36], intramolecularly coordinated organoelement compounds of types (A) -(E) (Figure 1) [37,38].…”