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Tris(pentafluoroethyl)indane dihydrate, [In(C2F5)3(OH2)2], and the gallium analog, [Ga(C2F5)3(OH2)2], serve as transfer reagents for the In(C2F5)3 and Ga(C2F5)3 units, as illustrated by the preparation of salts of (pseudo)halogenotris(pentafluoroethyl)indate and ‐gallate anions, [M(C2F5)3)X]− (M=Ga, In; X=F, Cl, Br, I, CN, SCN). Due to the water tolerance and water solubility of [In(C2F5)3(OH2)2] and [Ga(C2F5)3(OH2)2], reactions can be performed in the presence of water or even in an aqueous medium. [ABSTRACT FROM AUTHOR]

The introduction of a number of unsaturated fluorinated and chlorinated substituents onto gallium and indium was investigated. Gallate, [GaR4]−, and indate, [InR4]−, anions with trifluorovinyl (CF=CF2), 1‐chloro‐2,2‐difluorovinyl (CCl=CF2), (E)‐pentafluoropropen‐1‐yl (E‐CF=CFCF3), 3,3,3‐trifluoropropynyl (C≡C−CF3) and dichloromethyl (CHCl2) substituents were synthesized and isolated as the respective tetraphenylphosphonium salts. The respective gallate and indate salts were characterized by various methods, including NMR spectroscopy, mass spectrometry and X‐ray diffraction analysis. The generation of the respective organyllithium reagents, required for the syntheses of the gallate and indates, was performed starting from commercially available materials. This series of novel gallate and indate salts extends the chemistry of electron withdrawing groups to gallium and indium compounds. [ABSTRACT FROM AUTHOR]

Electron‐withdrawing substituents R in complexes [Ln M(PR2)] influence the P–M bond length due to a decreased σ‐donation and enhanced π‐back‐bonding, leading to an increased Lewis acidity of the metal ion and therefore strengthening the M–L bond to electron‐rich ligands L. This influences the Lewis acidity and the redox behavior of corresponding transition‐metal complexes, which is important for the design of optimized catalytic systems. To investigate this effect, the electron‐poor phosphanes R2PH with R = C2F5, C6F5, 2,4‐(CF3)2C6H3 were treated with Pd(F6acac)2 (F6acac = hexafluoroacetylacetonato) and Pd(acac)2 (acac = acetylacetonato). While the reaction of the phosphanes with Pd(F6acac)2 in all cases yielded the corresponding phosphido‐bridged dinuclear palladium complexes [{(F6acac)Pd[µ‐(PR2)]}2], the compounds obtained in the reaction with Pd(acac)2 were structurally more diverse. For R = C2F5, the dinuclear palladium complex [{(acac)Pd{µ‐[P(C2F5)2]}}2] was obtained, while the reaction with (C6F5)2PH yielded a trinuclear palladium complex bridged by four phosphido units. All complexes were fully characterized, including X‐ray crystallography. [ABSTRACT FROM AUTHOR]

In this contribution the syntheses of transition metal complexes of the electron‐withdrawing Sn(C2F5)3 ligand are presented. The reaction of HSn(C2F5)3 with organometallics LnM–R (M = Zn, W, Mo; R = Et, Me; L = CO, Cp), metal carbonyls [Ni(CO)4], and [{Fe(CO)2Cp}2], as well as chloro complexes such as [TiCl2Cp2], furnished the corresponding stannylated compounds. The electron‐deficient Sn(C2F5)3 ligand significantly influences the IR spectroscopic and structural features with respect to related non‐fluorinated stannyl complexes. [ABSTRACT FROM AUTHOR]

The reaction of the industrial product (C2F5)3PF2 with LiAlH4 in THF solution selectively furnished the hydridophosphate anion [P(C2F5)3F2H]-. The compound [PPh4][P(C2F5)3F2H] is obtained as a colorless solid on a multigram scale by salt metathesis in aqueous THF. Combining [P(C2F5)3F2H]- with various imidazolium and pyridinium cations affords ionic liquids with melting points well below room temperature. (C2F5)3PF2 also abstracts hydrides from amines, affording the hydridophosphate anion [P(C2F5)3F2H]- and the corresponding imminium cations which add a second amine moiety by intra- or intermolecular adduct formation. [ABSTRACT FROM AUTHOR]

Many approaches to introduce the CF2P(O)(OR)2 unit into organic molecules make use of CuI-catalyzed couplings between organic halides and BrZnCF2P(O)(OR)2. Despite the great importance of this process for the synthesis of α,α-difluoromethylenephosphonates, the constitution and molecular structures of the organozinc precursor and the catalytically relevant copper/zinc complex are still unknown. Here we report on the isolation of these two species, their spectroscopic characterization, and the determination of their structure by single-crystal X-ray diffraction. First orienting experiments on the stability of the cuprate reagent in solution at room temperature as well as its reactivity towards allyl bromides were subsequently performed. [ABSTRACT FROM AUTHOR]

The reaction of the industrial product (C2F5)3PF2 with LiAlH4 in THF solution selectively furnished the hydridophosphate anion [P(C2F5)3F2H]-. The compound [PPh4][P(C2F5)3F2H] is obtained as a colorless solid on a multigram scale by salt metathesis in aqueous THF. Combining [P(C2F5)3F2H]- with various imidazolium and pyridinium cations affords ionic liquids with melting points well below room temperature. (C2F5)3PF2 also abstracts hydrides from amines, affording the hydridophosphate anion [P(C2F5)3F2H]- and the corresponding imminium cations which add a second amine moiety by intra- or intermolecular adduct formation. [ABSTRACT FROM AUTHOR]

Electron‐withdrawing substituents R in complexes [Ln M(PR2)] influence the P–M bond length due to a decreased σ‐donation and enhanced π‐back‐bonding, leading to an increased Lewis acidity of the metal ion and therefore strengthening the M–L bond to electron‐rich ligands L. This influences the Lewis acidity and the redox behavior of corresponding transition‐metal complexes, which is important for the design of optimized catalytic systems. To investigate this effect, the electron‐poor phosphanes R2PH with R = C2F5, C6F5, 2,4‐(CF3)2C6H3 were treated with Pd(F6acac)2 (F6acac = hexafluoroacetylacetonato) and Pd(acac)2 (acac = acetylacetonato). While the reaction of the phosphanes with Pd(F6acac)2 in all cases yielded the corresponding phosphido‐bridged dinuclear palladium complexes [{(F6acac)Pd[µ‐(PR2)]}2], the compounds obtained in the reaction with Pd(acac)2 were structurally more diverse. For R = C2F5, the dinuclear palladium complex [{(acac)Pd{µ‐[P(C2F5)2]}}2] was obtained, while the reaction with (C6F5)2PH yielded a trinuclear palladium complex bridged by four phosphido units. All complexes were fully characterized, including X‐ray crystallography. [ABSTRACT FROM AUTHOR]

In this contribution the syntheses of transition metal complexes of the electron‐withdrawing Sn(C2F5)3 ligand are presented. The reaction of HSn(C2F5)3 with organometallics LnM–R (M = Zn, W, Mo; R = Et, Me; L = CO, Cp), metal carbonyls [Ni(CO)4], and [{Fe(CO)2Cp}2], as well as chloro complexes such as [TiCl2Cp2], furnished the corresponding stannylated compounds. The electron‐deficient Sn(C2F5)3 ligand significantly influences the IR spectroscopic and structural features with respect to related non‐fluorinated stannyl complexes. [ABSTRACT FROM AUTHOR]