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Published on: December 16, 2013
Li/X phosphinidenoid pentacarbonylmetal complexes: a combined experimental and theoretical study on structures and
Rainer Streubel1, Aysel Özbolat-Schön, Gerd von Frantzius
1Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121 Bonn, Germany. r.streubel@uni-bonn.de
Abstract:
The synthesis of P-F phosphane metal complexes [(CO)5M{RP(H)F}] 2a-c (R = CH(SiMe3)2; a: M = W; b: M = Mo; c: M = Cr) is described using AgBF4 for a Cl/F exchange in P-Cl precursor complexes [(CO)5M{RP(H)Cl}] 3a-c; thermal reaction of 2H-azaphosphirene metal complexes [(CO)5M{RP(C(Ph)═N}] 1a-c with [Et3NH]X led to complexes 3a-c, 4, and 5 (M = W; a-c: X = Cl; 4: X = Br; 5: X = I). Complexes 2a-c, 3a-c, 4, and 5 were deprotonated using lithium diisopropylamide in the presence of 12-crown-4 thus yielding Li/X phosphinidenoid metal complexes [Li(12-crown-4)(Et2O)n][(CO)5M(RPX)] 6a-c, 7a-c, 8, and 9 (6a-c: M = W, Mo, Cr; X = F; 7a-c: M = W, Mo, Cr; X = Cl; 8: M = W; X = Br; 9: M = W; X = I). This first comprehensive study on the synthesis of the title compounds reveals metal and halogen dependencies of NMR parameters as well as thermal stabilities of 6a, 7a, 8, and 9 in solution (F > Cl > Br > I). DOSY NMR experiments on the Li/F phosphinidenoid metal complexes (6a-c; M = W, Mo, Cr) rule out that the cation and anion fragments are part of a persistent molecular complex or tight ion pair (in solution). The X-ray structure of 6a reveals a salt-like structure of [Li(12-crown-4)Et2O][(CO)5W{P(CH(SiMe3)2)F}] with long P-F and P-W bond distances compared to 2a. Density functional theory (DFT) calculations provide additional insight into structures and energetics of cation-free halophosphanido chromium and tungsten complexes and four contact ion pairs of Li/X phosphinidenoid model complexes [Li(12-crown-4)][(CO)5M{P(R)X}] (A-D) that represent principal coordination modes. The significant increase of the compliance constant of the P-F bond in the anionic complex [(CO)5W{P(Me)F}] (10a) revealed that a formal lone pair at phosphorus weakens the P-F bond. This effect is further enhanced by coordination of lithium and/or the Li(12-crown-4) countercation (to 10a) as in type A-D complexes. DFT calculated phosphorus NMR chemical shifts allow for a consistent interpretation of NMR properties and provide a preliminary explanation for the "abnormal" NMR shift of P-Cl derivatives 7a-c. Furthermore, calculated compliance constants reveal the degree of P-F bond weakening in Li/F phosphinidenoid complexes, and it was found that a more negative phosphorus-fluorine coupling constant is associated with a larger relaxed force constant.
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