17-Sep-21 News Extracurricular laboratory:new discovery of 1,1′-Bis(diisopropylphosphino)ferrocene

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Reactions of N,N’-di-n-butyl-2-amino-5-alcoholate-1,4- benzoquinonemonoiminium L1, or N,N’-diisopropyl-2-amino-5- al?holate-1,4-benzoquinonemonoiminium L2 with [{(dppf)Cu} 2(mu-CI)2] (dppf = 1,1′-bis(diphenylphosphino)ferrocene) or [{(dispf)Cu}2(mu-Cl)2] (dispf = 1,1 ‘-bis(diisopropylphosphino)ferrocene) led to the formation of the heterodinuclear complexes [(dppf)(CuL1-H)] (2), [(dppf)(CuL2-H)] (3), [(dispf)(CuL1- H)] (4), and [(dispf)(CuL2-H)] (5). The crystal structure of L2 was determined by X-ray diffraction and shows that the molecule exists in a 6pi + 6pi zwitterionic form, with two chemically connected but electronically nonconjugated pi-subunits. The crystal structures of complexes 2-4 show a distorted tetrahedral coordination environment for the Cu(l) center and a more localized pi-system for the ligands. Cyclic voltammetry on the ligands and complexes indicates various redox processes. The first oxidation of the complexes leads to an electron paramagnetic resonance supported formulation where the ligand radical is bound to Cu(l). UV-visible spectroscopy of the ligands and the complexes is also reported and discussed.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The crystal structure of [Ir(cod)(L-L)]+ 3 [cod = cycloocta-1,5-diene, L-L = 1-(diisopropylphosphino)-1?-(diphenylphosphino)ferrocene] can be related to those of the analogous complexes with L-L =1,1?-bis(diphenylphosphino)ferrocene (dppf) 1 and 1,1?-bis(diisopropylphosphino)ferrocene (disppf), 2, all the complexes being readily synthesized from [Ir(cod)(py)2]+ (py = pyridine). An optimum diphosphine bite angle of approximately 99 is maintained in all three complexes by varying the twist of the ferrocene, which decreases with increasing steric profile of the phosphine, and by distortion of the geometry at the iridium atom away from square planar towards tetrahedral. The twist about the ferrocene moiety induces chirality at the iridium atom in all three complexes and the interchange of stereoisomers can be followed by variable-temperature 1H NMR spectroscopy. Application of the Eyring equation gave approximate values of DeltaG? for this process of 36.1 ± 0.2, 39.3 ± 0.2 and 34.3 ± 0.2 kJ mol-1 for 1-3 respectively. The ligand disoppf also induces considerable distortion away from square-planar geometry in the complex [Rh(nbd)(disoppf)][BF4]4 {nbd = norbornadiene (bicyclo[2.2.1]hepta-2,5-diene)}, as found in a crystal structure determination, which may account for the unusual lability of the chelating diphosphine. This is demonstrated by its reactions with Ph2P(CH2)nPPh2 (n = 1 or 2) both of which give [Rh(L-L)2]+. More surprisingly, considering its lability in [Rh(nbd)(dppf)]+, dppf also readily displaced disoppf from 4, to give [Rh(nbd)(dppf)][BF4] 5. The nbd ligand in this complex is not displaced by reaction with an excess of dppf.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Reaction of [(dppf)Au2Br2] (3) {dppf = 1,1?-bis(diphenylphosphino)ferrocene} and [(dippf)Au2Br2] (4) {dippf = 1,1?-bis(diisopropylphosphino)ferrocene} with excess bromine yields two new complexes [(C5H4Br3)(PR2)AuBr] (R = Ph, 5; R = i-Pr, 6). Bromination of the free diphosphinoferrocene ligands produces the expected brominated cyclopentenes (C5H4Br3)(PR2) (R = Ph, 7; R = i-Pr, 8) in good yields; however, these compounds could not be complexed to gold due to reduced basicity of 7 and 8. When the bromination is performed under wet aerobic conditions the oxidized pseudo-centrosymmetric product, [doppf][FeBr4] (9) {doppf = 1,1?-bis(oxodiphenylphosphino)ferrocene, is formed as the major product. Solid-state structures of 1, 2, 4, 6, and 9 have been established by means of single-crystal X-ray crystallography.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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A low-valent cobalt catalyst generated from cobalt(II) bromide, a diphosphine ligand, and zinc powder promotes intermolecular hydroacylation of olefins using N-3-picolin-2-yl aldimines as aldehyde equivalents, which affords, upon acidic hydrolysis, ketone products in moderate to good yields with high linear selectivity. The reaction is applicable to styrenes, vinylsilanes, and aliphatic olefins as well as to various aryl and heteroaryl aldimines. The cobalt catalysis features a distinctively lower reaction temperature (60 C) compared with those required for the same type of transformations catalyzed by rhodium complexes (typically 130-150C).

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The oxidative electrochemistry of group VI and group VII metal carbonyl compounds containing 1,1?-bis(phosphino)ferrocene ligands with the general formula [M(CO)4(P?P)] (M = Cr, Mo, or W, P ?P = 1,1?-bis(diisopropylphosphino)ferrocene (dippf) or 1,1?-bis(dicyclohexylphosphino)ferrocene (dcpf)) and [M(CO) 3Br(P?P)] (M = Mn, P?P = 1,1?-bis(diphenylphosphino)ferrocene (dppf) or dippf; M = Re, P ?P = dppf, dippf or dcpf) was investigated. Two reversible waves were observed in the electrochemistry of the Cr compounds, while the other compounds exhibited one wave with varying reversibility. The compounds were examined using spectroelectrochemistry, which was particularly useful in assigning the two waves in the Cr species. In addition, the X-ray structures of [Cr(CO)4(dippf)], [Cr(CO)4(dcpf)] and [Mn(CO) 3Br(dippf)] were determined. The %Vbur values for dippf, dcpf and other bidentate phosphines have been calculated for these pseudo-octahedral Cr and Mn compounds and these structural studies have been supplemented by DFT optimized geometries for the Cr complexes.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The present invention relates to a selective method for carrying out the Buchwald-Hartwig coupling of biphenyl derivatives.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Mono- and bis-phosphinoferrocenes are shown to react as frustrated Lewis pairs (FLPs) to effect nucleophilic aromatic substitution on B(C 6F5)3 and/or activate H2 to form ferrocenylphosphonium borates. The Royal Society of Chemistry 2009.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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Detailed mechanistic studies on the coupling of aryl halides with thiolscatalyzed by palladium complexes of the alkylbisphosphine ligand CyPF- t Bu (1-dicyclohexylphosphino-2-di-tert-butylphosphinoethylfer rocene) are reported. The elementary steps that constitute the catalyticcycle, i.e. oxidative addition, transmetalation and reductive eliminati on, have been studied, and their relative rates are reported. Each of the steps of the catalytic process occurs at temperatures that are much lower than those required for the reactions catalyzed by a combination of palladium precursors and CyPF- t Bu. To explain these differences in rates between the catalytic and stoichiometric reactions, studies were conducted to identify the resting state of the catalyst of the reactions catalyzed by a combination of Pd(OAc)2 and CyPF- t Bu, a combination of Pd(dba) 2 and CyPF- t Bu, or the likely intermediate Pd(CyPF- t Bu)(Ar)(Br). These data show that the major palladium complex in each case lies off of the catalytic cycle. The resting state of the reactions catalyzed by Pd(OAc) 2 andCyPF- t Bu was the palladium bis-thiolate complex [Pd(CyPF-t Bu)(SR) 2 ] (R = alkyl or aryl). The resting state in reactions catalyzed by Pd 2 (dba) 3 and CyPF- t Bu was the binuclear complex [Pd(CyPF t Bu)] 2 (mu 2 ,eta 2 -dba) (9). The resting states of reactions of both aromatic and aliphatic thiols catalyzed by [Pd(CyPF- t Bu)(p-tolyl)(Br)] (3a) were the hydridopalladium thiolate complexes [Pd(CyPF- t Bu)(H)(SR)] (R= alkyl and aryl). All these palladium species have been prepared independently, and the mechanisms by which they enter the catalytic cycle have been examined in detail. These features of the reaction catalyzed by palladium and CyPF- t Bu have been compared with those of reactions catalyzed by the alkylbisphosphine DiPPF and Pd(OAc) 2 or Pd(dba) 2 . Our data indicate that the resting states of these reactions are similar to each otherand that our mechanistic conclusions about reactions catalyzed by palla dium and CyPF- t Bu can be extrapolated to reactions catalyzed by complexes of other electron-rich bisphosphines.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The complex cations [Cu(dippf)(DML)]+ ([1]+) and [Cu(dppf)(DML)]+ ([2]+), where dippf = 1,1?-bis(diisopropylphosphino)ferrocene, dppf = 1,1?-bis-(diphenylphosphino)ferrocene, and DML = 1,3-dimethyllu-mazine, were prepared and crystallized as BF4- or PF6- salts. Structure determinations of the tetrafluoroborates revealed asymmetric O4,N5 chelation of DML to copper(I) with longer Cu-O bonds of about 2.25 a. Reversible oxidation to [1]2+ and [2]2+ proceeds at the ferrocene units, while reduction leads to the neutral radical complexes [1] and [2] with the unpaired electron localized on the DML ligand. The occurrence of two voltammetric steps for the one-electron-reduction process is attributed to a two-species equilibrium caused by the hemilabile coordination of DML. Electrochemical and spectroelectrochemical measurements (UV-vis, IR) reveal increased coordination lability of the reduced complexes and their slow fragmentation. (Figure Presented)

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

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The chemoselective generation of aldehyde-derived enolates to realize an aldehyde – aldehyde cross-aldol reaction is described. A combined Rh/dippf system efficiently promoted the isomerization/aldol sequence by using primary allylic, homoallylic, and bishomoallylic alcohols; secondary allylic and homoallylic alcohols; and trialkoxyboranes that were derived from primary allylic and homoallylic alcohols. The reaction proceeded at ambient temperature under base-free conditions, thus giving cross-aldol products with high chemoselectivity. Mechanistic studies, as well as its application to double-aldol processes under protecting-group-free conditions, are also described. Copyright

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate