163454-36-2Relevant academic research and scientific papers
Reactions of Cp′(CO)2MnPPh2H with CH3COCl and CH3S(O)2Cl in THF/triethylamine: Evidence of the first complex stabilization of a phosphorus homolog of the sulfonamides
Manzoni De Oliveira, Gelson,Seiffert, Milton,Lorenz, Ingo-Peter
, p. 101 - 105 (1999)
The complex Cp′Mn(CO)3 (Cp′=η5-C5H4-CH3) reacts with P(C6H5)2H in THF to give Cp′(CO)2MnPPh2H (Ph=phenyl) (1), by substitution of one CO ligand. The reaction of 1 with CH3COCl and CH3S(O)2Cl in the presence of triethylamine occurs under electrophilic substitution on the diphenylphosphane ligand yielding the acetyl and sulfonylphosphane complexes of manganese(I) Cp′(CO)2MnPPh2COCH3 (2) and Cp′(CO)2MnPPh2S(O)2CH3 (3). The complex stabilization of these molecules, which are hitherto unknown in the free state, is only accomplished by blocking the free electron pair on phosphorus by coordination. The new complexes 1, 2 and 3 were analyzed by IR, 1H and 31P NMR spectroscopy and their similar structures are discussed.
Formation and reactivity of transient phosphanoxyl manganese complexes
Heurich, Tobias,Naz, Nabila Rauf,Qu, Zheng-Wang,Schnakenburg, Gregor,Streubel, Rainer
, p. 3670 - 3677 (2018)
Formation of thermally unstable complexes [Mn(CO)2CpMe(R2PO-TEMP)] (Cp = cyclopentadienyl; Me = methyl; TEMP = 2,2,6,6-tetramethyl-piperidin-1-oxyl) is presented in this experimental and theoretical study; in case of R = Cy 31P NMR spectroscopic evidence is provided. Mechanistic details of the product formation and decomposition, due to a homolytic O-N bond cleavage, are revealed by high-level density functional theory calculations. Insights into stability and spin density distribution of transient phosphanoxyl complexes [Mn(CO)2CpMe(R2PO·)] and preliminary results on the acidity of related complexes [Mn-(CO)2CpMe(R2P-OH)] and [W(CO)5(R2P-OH)] toward TEMP-H are presented.
Phosphido bridged heterodinuclear (Mn/Fe, Mn/Cr, Mn/W) complexes
Lin, Jiann T.,Yeh, An C.,Chou, Yung C.,Tsai, Thomas Y. R.,Wen, Yuh S.
, p. 147 - 154 (2007/10/02)
Treatment of (MeCp)Mn(CO)2(Ph2PLi), generated in situ, with M(CO)n(THF) in THF at -60 deg C followed by cation exchange, provides (3, M = Fe, n = 4; 5, M = Cr, n = 5; 6, M = W, n = 5).Complex 3 reacts with NO+BF4- to give (MeCp)MnFe(CO)4(NO)(μ-PPh2) (7) which contains a metal-metal (Mn-Fe) bond.Photolysis of 6 also results in formation of a metal-metal bond, and (8) was isolated.Complex 8 reacts with CO and MeNC to afford 6 and (9), respectively.X-raydiffraction studies of (μ-Ph2PPPh2) (4), 6, and 9 were carried out to give data as follows. 4: P21/n, Z=4, a = 9.6875(9), b = 12.191(1), c = 15.382(2) Angstroem, β = 107.20(1) deg, V = 1735.4(4) Angstroem, R = 0.032, Rw = 0.036. 6: Pbca, Z=8, a = 13.197(2), b = 20.544(4), c = 24.953(4) Angstroem, V = 6765(2) Angstroem, R = 0.031, Rw = 0.031. 9: P21/c, Z=4, a = 14.252(1), b = 12.816(3), c = 19.176(2) Angstroem, β = 96.255(9) deg, V = 3481.6(9) Angstroem, R = 0.035, Rw = 0.038.Keywords: Iron; Manganese; Chromium; Phosphide; Heterobimetallics; Metal carbonyl anions
