0000000000459613
AUTHOR
Florian P. Pruchnik
Orthometallation reactions of tris(p-methoxyphenyl)phosphine with dirhodium(II) tetraacetate
Abstract Reactions of dirhodium(II)tetraacetate [Rh2(OAc)4] with tris(p-methoxyphenyl)phosphine (PMP) at 1:1 and 1:2 molar ratios yield, first appropriate adducts: [Rh2(OAc)4P(p-CH3OC6H4)3] (1a) and [Rh2(OAc)4{P(p-CH3OC6H4)3}2] (2a), and then orthometallated [Rh2(OAc)3{μ-(p-CH3OC6H3)P(p-CH3OC6H4)2}(HOAc)2] (1) and [Rh2(OAc)2{μ-(p-CH3OC6H3)P(p-CH3OC6H4)2}2(HOAc)2] (2) complexes, respectively. They have been characterized by spectroscopic methods. The molecular structure of 1 has been determined by the X-ray methods. Crystal data: space group P1, a=11.085(5), b=11.387(5), c=13.900(6) A, α=97.29(3), β=105.23(3), γ=91.93(3)°. In this compound The Rh–Rh distance is 2.421(1), Rh–P bond length 2.1…
Orthometalation of Tris(3-sodium sulfonatophenyl)phosphine with Dirhodium(II) Acetate
Tetraacetatodirhodium(II) reacts with tris(3-sodium sulfonatophenyl)phosphine (TPPTS) giving [Rh2(μ-OOCCH3)3{μ-(3-NaO3SC6H3)P(C6H4SO3Na-3)2}(HOOCCH3)]·6H2O (1) and [Rh2(μ-OOCCH3)2{μ-(3-NaO3SC6H3)P(C6H4SO3Na-3)2}2(HOOCCH3)]·12H2O (2). Their structures and properties have been studied by electronic, IR, and 31P{1H}, 1H, 1H{31P}, and 13C{1H} NMR spectroscopies. In compound 1, one of the acetate bridges is replaced by a phosphine ligand, orthometalated via the C2 carbon atom of the phenyl ring. One axial site of the Rh24+ core is occupied by a sulfonato group of the metalated ring and another one by a labile molecule of acetic acid. 1H NMR spectroscopy shows that chemical shifts of the aromatic…