1219040-94-4Relevant articles and documents
Hydridic reactivity of W(CO)(H)(NO)(PMe3)3 - Dihydrogen bonding and H2 formation with protic donors
Avramovi?, Nata?a,H?ck, Jürgen,Blacque, Olivier,Fox, Thomas,Schmalle, Helmut W.,Berke, Heinz
, p. 382 - 391 (2010/04/27)
The hydridic reactivity of the complex W(CO)(H)(NO)(PMe3)3 (1) was investigated applying a variety of protic donors. Formation of organyloxide complexes W(CO)(NO)(PMe3)3(OR) (R = C6H5 (2), 3,4,5-Me3C6H2 (3), CF3CH2 (4), C6H5CH2 (5), Me (6) and iPr (7)) and H2 evolution was observed. The reactions of 1 accelerated with increasing acidity of the protic donor: Me2CHOH (pKa = 17) a = 15.5) 6H5CH2OH (pKa = 15) 3CH2OH (pKa = 12.4) 6H2Me3OH (pKa = 10.6) 6H5OH (pKa = 10). Regioselective hydrogen bonding of 1 was probed with two of the protic donors furnishing equilibrium formation of the dihydrogen bonded complexes ROH···HW(CO)(NO)(PMe3)3 (R = 3,4,5-Me3C6H2, 3a and iPr, 7a) and the ONO hydrogen bonded species ROH···ONW(CO)(H)(PMe3)3 (R = C6H2Me3, 3b and iPr, 7b) which were studied in hexane and d8-toluene solutions using variable temperature IR and NMR spectroscopy. Quantitative IR experiments at low temperatures using 3,4,5-trimethylphenol (TMP) confirmed the two types of competitive equilibria: dihydrogen bonding to give 3a (ΔH1 = -5.8 ± 0.4 kcal/mol and ΔS1 = -15.3 ± 1.4 e.u.) and hydrogen bonding to give 3b (ΔH2 = -2.8 ± 0.1 kcal/mol and ΔS2 = -5.8 ± 0.3 e.u.). Additional data for the hydrogen bonded complexes 3a,b and 7a,b were determined via NMR titrations in d8-toluene from the equilibrium constants K(Δδ) and K(Δ R1) measuring either changes in the chemical shifts of HW(Δδ) or the excess relaxation rates of HW (ΔR1) (3a,b: ΔH(Δδ) = -0.8 ± 0.1 kcal/mol; ΔS(Δδ) = -1.4 ± 0.3 e.u. and Δ H(Δ R1) = -5.8 ± 0.4 kcal/mol; Δ S(Δ R1) = -22.9 ± 1.9 e.u) (7a,b: ΔH(Δδ) = -2.3 ± 0.2 kcal/mol; ΔS(Δδ) = -11.7 ± 0.9 e.u. and Δ H(Δ R1) = -2.9 ± 0.2 kcal/mol; Δ S(Δ R1) = -14.6 ± 1.0 e.u). Dihydrogen bonding distances of 1.9 A? and 2.1 A? were derived for 3a and 7a from the NMR excess relaxation rate measurements of HW in d8-toluene. An X-ray diffraction study was carried out on compound 2.