Synthesis, Structure and Reactivity of [1, 2‐Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I) with Reactions of Phosphites, Phosphonites. and Phosphinites

Abstract

The manganese carbonyl complex [MnBr(CO)3L] (1), where L = Ph2POCH2CH2OPPh2, was prepared by reacting [MnBr(CO)5] with the bidentate ligand 1, 2‐Bis(diphenylphosphinite)ethane. From this compound and the appropriate phosphite, phosphinite or phosphonite ligands were synthesized the complexes [MnBr(CO)2LL′], where L′ = P(OMe)3 (2) or P(OEt)3 (3) and [MnBr(CO)3L′2], where L′ =PPh(OEt)2 (4) or PPh2(OEt) (5).The obtained compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR (1H, 13C and 31P) spectroscopies and X‐ray diffractometry for the complexes 1, 4 and 5.

Tricarbonyl Derivatives of Manganese(I) with Diphosphinite Chelating Ligands

“…Besides, the CO ligands trans to Br or Cl are closer to the Mn atom, as expected from the π-donor character of the halogen [e.g. 1.775(4) vs. 1.807(4) and 1.803(4) Å in the chloro-, 1.805 (7) vs. 1.835(6) and 1.841(7) Å in the bromo-complex]. Similarly, the Mn-C bond lengths for the CO ligands trans to oxygen are 1.769 (4) showing that the number of members of the chelating ring involved in this bond is great enough to induce no significant steric hindrance in the bidentate phosphane ligand.…”

“…Deuterated solvent (CDCl 3 Merck) for NMR measurements was dried over molecular sieves. 1,2-Bis(diphenylphosphinoxy)ethane and 1,2 bis(diisopropylphosphinoxy)ethane were prepared as described previously [9], [MnBr(CO) 5 ] was obtained from [Mn 2 (CO) 10 ] by the method described in literature [10] and the starting product [MnBr(CO) 3 L 1 ] has been previously reported [7]. AgSO 3 CF 3 , AgCO 2 CF 3 (Aldrich), CH 3 CN, KCN and KSCN (Merck) were used as supplied.…”

“…In a previous work [7], we reported the synthesis of a series of complexes resulting from the substitution of two CO ligands from [MnBr(CO) 5 ] for a variety of phosphite, phosphonite and phosphinite bidentate ligands. By using two of those complexes as starting material, we carried out the abstraction of Br and its substitution for triflate and trifluoroacetate ligands.…”

Syntheses of gyroscope-like molecules via three-fold ring closing metatheses of bis(phosphine) complexes trans-LyM(P((CH2)nCHCH2)3)2, and extensions to bis(phosphite) complexes trans-Fe(CO)3(P(O(CH2)nCHCH2)3)2

“…In contrast to the free phosphites, the latter were not detectably coupled to phosphorus. Other researchers have noted both broad singlets and resolved doublets for the POCH 2 CH 2 signals of phosphite complexes [30]. The 13 C NMR spectra also showed a single peak for the CO ligands (212.2-213.0 ppm), in two cases with resolved phosphorus coupling ( 2 J CP = 39.8-39.5 Hz).…”

New Dinuclear Face‐ and Edge‐Sharing Bioctahedral Ruthenium Compounds Containing 1,2‐Bis(diphenylphosphanyloxy)ethane

“…A similar situation occurs with the signals corresponding to the methylene groups of the bidentate ligand. As observed in other halide compounds bearing this ligand, [11] these groups usually display one multiplet for each proton. In our case different multiplets were observed that integrate as one proton each and these coexist with other signals of lower intensity that may correspond to the cisoid structure.…”