170656-69-6Relevant articles and documents
Variable coordination modes for 1,1′-bis (diphenylphosphino) ferrocene (dppf) mono-and di-chalcogenides or -oxides (dppfE and dppfE2; E = O, S or Se) in copper(I) complexes. Crystal structure of [{Cu(dppf)}2(μdppfS2)] (BF4)2 and [Cu(dppfSe)2]BF4
Pilloni, Giuseppe,Longato, Bruno,Bandoli, Giuliano
, p. 163 - 170 (1998)
Reaction of [Cu(MeCN)4]BF4 with the phosphine Fe[η5-C5H4PPh2]2 (dppf) and its disulfide (dppfS2) sequentially in chlorinated solvents led to the dinuclear tricoordinate complex [{Cu(dppf-P,P′)}2(μ-dppfS2-S,S′)] (BF4)2 (1), whereas reaction of the copper reagent with dppf and its diselenide (dppfSe2) gave the bis-chelate dppf-monoselenide compound [Cu(dppfSe-P,Se)2]BF4 (2). Similarly, the E = O or S relevant complexes [Cu(dppfE-P,E)2]BF4 were obtained by reaction of the copper(I) precursor with the dppf-monoderivatives [η5-C5H4PPh2]Fe[η 5-C5H4P(E)Ph2] (dppfE). The complexes have been characterized by 1H and 31P NMR spectroscopy. Single-crystal X-ray structure determinations were performed for complexes 1 and 2. Complex 1 crystallizes as CHCl3 (1a) or CHBr3 (1b) monosolvates. The cation of 1 is exactly centrosymmetric and shows a distorted trigonal planar coordination at copper with a P-Cu-P angle of 115.7(1)° and the S-Cu-P angles of 138.6(1) and 104.3(6)°, as mean values from 1a and 1b. In complex 2 the coordination geometry around the metal atom is markedly distorted tetrahedral with the two dppfSe moieties acting as chelating ligands with bite angles of 111.5(2) and 116.8(2)°. The Se(1)-Cu-Se(2) angle (103.4(2)°) approaches the value for tetrahedral geometry, while the remaining angles differ significantly from the ideal value ranging from 96.1(2) to 121.9(3)°. The Cu-Se-P angles (124.5(2) and 132.9(2)°) point towards a substantially sp2 hybridization of the selenium atom.
Molecular structures of 1,1'-bis(diphenylphosphino)ferrocene oxide and sulphide and their thermal properties
Fang, Zhi-Gang,Hor, T. S. Andy,Wen, Yuh-Sheng,Liu, Ling-Kang,Mak, Thomas C. W.
, p. 2403 - 2410 (1995)
The crystal and molecular structure of anhydrous 1,1'-bis(diphenylphosphino)ferrocene sulphide, Fe[C5H4P(S)Ph2]2 (dppfS2), is reported and compared with the hydrated oxide analogue, Fe[C5H4P(O)Ph2]2*2H2O (dppfO2*2H2O). It consits of two phosphoryl cyclopentadienyl rings [P-S =1.938(2) ?] sandwiching an Fe(II) centre. With four molecules per cell, the molecule is crystallographically required to sit on an inversion centre andhence the two rings are staggered. The thermal properties of [Fe(C5H4PP h2)2] (dppf), dppfO2*2H2O and dppfS2 were studied together with Fe(Cp)2 and Ph3PO*H2O by TGA and DSC. The thermal stability decreases in the order dppfO2>dppf>dppfS2. The hydrogen-bonded hydrate in dppfO2*2H2O is removed upon heating to 110-160°C.
Sulfur-controlled and rhodium-catalyzed formal (3 + 3) transannulation of thioacyl carbenes with alk-2-enals and mechanistic insights
Wu, Qiuyue,Dong, Ziyang,Xu, Jiaxi,Yang, Zhanhui
supporting information, p. 3173 - 3180 (2021/04/21)
A rhodium-catalyzed denitrogenative formal (3 + 3) transannulation of 1,2,3-thiadiazoles with alk-2-enals is achieved, producing 2,3-dihydrothiopyran-4-ones in moderate to excellent yields. An inverse KIE of 0.49 is obtained, suggesting the reversibility of the oxidative addition of thioacyl Rh(i) carbenes to alk-2-enals. The late-stage structural modifications of steroid compounds are realized. Moreover, our studies show that thioacyl carbenes have different reactivities to those of α-oxo and α-imino carbenes, and highlight the importance of heteroatoms in deciding the reactivities of heterovinyl carbenes.
Synthesis, Characterization, and Reactivity of Functionalized Trinuclear Iron-Sulfur Clusters - A New Class of Bioinspired Hydrogenase Models
Kaiser, Manuel,Kn?r, Günther
, p. 4199 - 4206 (2015/09/15)
The air- and moisture-stable iron-sulfur carbonyl clusters Fe3S2(CO)7(dppm) (1) and Fe3S2(CO)7(dppf) (2) carrying the bisphosphine ligands bis(diphenylphosphanyl)methane (dppm) and 1,1′-bis
Comparative reactivity studies of dppf-containing CpRuII and (C6Me6)RuII complexes towards different donor ligands (dppf=1,1′-bis(diphenylphosphino)ferrocene)
Lu, Xiu Lian,Vittal, Jagadese J.,Tiekink, Edward R.T.,Tan,Kuan, Seah Ling,Goh, Lai Yoong,Hor, T.S. Andy
, p. 1978 - 1990 (2007/10/03)
[CpRu(dppf)Cl] (Cp=η5-C5H5) (1) and [(HMB)Ru(dppf)Cl]PF6 ((HMB)=η6-C6Me6) (3) react with different donor ligands to give rise to N-, P- and S-bonded complexes. The stoichiometric reactions of 1 and 3 with NaNCS give the mononuclear complexes [CpRu(dppf)(NCS)] (2) and [(HMB)Ru(dppf)(NCS)]PF6 (4), respectively, in yields above 80%, while 3 also gives a dppf-bridged diruthenium complex [(HMB)Ru(NCS)2]2 (μ-dppf) (5) in 67% yield from reaction with four molar equivalents of NaNCS. Compound 5 is also obtained in 70% yield from the reaction of 4 with excess NaNCS. With CH3CN in the presence of salts, both 1 and 3 give their analogous solvento derivatives [CpRu(dppf) (CH3CN)] BPh4 (6) and [(HMB)Ru(dppf) (CH3CN)] (PF6)2 (7). With phosphines, the reaction of 1 gives chloro-displaced complexes [(CpRu(dppf)L]PF6 (L =PMe3 (8), PMe2Ph(9), whereas the reaction of 3 with PMe2Ph leads to substitution of dppf, giving [(HMB)Ru(PMe2Ph)2Cl] PF6 (10). The reaction of 1 with NaS2CNEt2 gives a dinuclear dppf-bridged complex [{CpRu(S2CNEt2)} 2(μ-dppf)] (11), whereas that of 3 results in loss of the HMB ligand giving a mononuclear complex [Ru(dppf) (S2CNEt2)2] (12). With elemental sulfur S8, 1 is oxidized to give a dinuclear CpRuIII dppf-chelated complex [{CpRu(dppf)}2(μ-S2)] (BPh4)Cl (13), whereas 3 undergoes oxidation at the ligand, giving a dppf-displaced complex [(HMB)Ru(CH3CN)2Cl] PF6 (14) and free dppfS2. The structures of 1, 2, 5-9, 11, 13 and 14 were established by X-ray single crystal diffraction analyses. Of these, 5 and 11 both contain a dppf-bridge between RuII centers, while 13 is a dinuclear CpRuIII disulfide-bridged complex; all the others are mononuclear. All complexes obtained were also spectroscopically characterized.
