Syntheses and Molecular Structures of [RSn{W(CO)₃Cp}₂][W(CO)₃Cp], [RSn{W(CO)₃Cp}Cl₂], and [RSn{W(CO)₃Cp}Cr(CO)₅] (R = [4-t-Bu-2,6-{P(O)(OR′)₂}₂C₆H₂], R′ = Et,i-Pr). Autoionization Induced by Intramolecular P═O→Sn Coordination

Abstract

The syntheses of the intramolecularly coordinated organotin-substituted transition metal complexes [RSn{W(COand [RSn{W(CO) 3 Cp}-Cr(CO) 5 ] (5, R = 4-t-Bu-2,6-{P(O)(OEt) 2 } 2 C 6 H 2 ) are reported. The reaction of compound 2 with Ph 4 P + Br¯gave the benzoxaphosphastannole [1(P),3(Sn)-Sn[W(CO) 3 Cp] 2 OP(O)(Oi-Pr)-6-t-Bu-4-P(O)(Oi-Pr) 2 -C 6 H 2 ] (3). The compounds are characterized by 1 H, 13 C, 31 P, 119 Sn NMR and IR spectroscopy and, except for 3, by single crystal X-ray diffraction analysis. The experimental work is accompanied by DFT calculations.

Reactive p-block cations stabilized by weakly coordinating anions

“… 383 The same ligand was used to prepare the [RSn{W(CO) 3 Cp} 2 ] + , with R = R = 4- t Bu-2,6-{P(O)(O i Pr) 2 } 2 C 6 H 2 ) and [W(CO) 3 Cp] – as its counterion. 384 Recently, new platinum-coordinated cations of tin and lead were published. Starting from (Cy 3 P) 2 Pt(SnBr 2 ), [{(Cy 3 P) 2 Pt-SnBr} 2 ] + was synthesized with two different anions.…”

The Role of Monoanionic Aryl Pincer Ligands in the Stabilization of Group 14 Metallylenes

“…2DME to its chromium complex L IV SnCl(Cr(CO)5) to form 127. [68] In the first case 124 [68] was formed through a spontaneous auto-ionization process of the intermediary L IV Sn{W(CO)3Cp}3 species. A ferrocenylbridged bis-stannylene 122 was obtained from stannylene 35 by adding 1,1'-dilithiumferrocenyl, as shown in Scheme 16.…”