Rhodium(I) carbonyl complexes of chalcogen functionalized tripodal phosphines, [CH3C(CH2P(X)Ph2)3] {X=O, S, Se} and their reactivity

Add time:09/29/2019    Source:infona.pl

The reaction of dimeric rhodium precursor [Rh(CO) 2 Cl] 2 with two molar equivalent of 1,1,1-tris(diphenylphosphinomethyl)ethane trichalcogenide ligands, [CH 3 C(CH 2 P(X)Ph 2 ) 3 ](L), where X=O(a), S(b) and Se(c) affords the complexes of the type [Rh(CO) 2 Cl(L)] (1a–1c). The complexes 1a–1c have been characterized by elemental analyses, mass spectrometry, IR and NMR ( 1 H, 31 P and 13 C) spectroscopy and the ligands a–c are structurally determined by single crystal X-ray diffraction. 1a–1c undergo oxidative addition (OA) reactions with different electrophiles such as CH 3 I, C 2 H 5 I and C 6 H 5 CH 2 Cl to give Rh(III) complexes of the types [Rh(CO)(COR)ClXL] {R=–CH 3 (2a–2c), –C 2 H 5 (3a–3c); X=I and R=–CH 2 C 6 H 5 (4a–4c); X=Cl}. Kinetic data for the reaction of a–c with CH 3 I indicate a first-order reaction. The catalytic activity of 1a–1c for the carbonylation of methanol to acetic acid and its ester is evaluated and a higher turn over number (TON=1564–1723) is obtained compared to that of the well-known commercial species [Rh(CO) 2 I 2 ] − (TON=1000) under the reaction conditions: temperature 130±2°C, pressure 30±2bar and time 1h.

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