Synthesis and Characterization of Tetrakis(pentafluoroethyl)indate Salts.

In the rising field of organoindium chemistry little is known about the perfluoroorganyl-substituted indium compounds. The increasing use of indium reagents is explained by their high stability and tolerance towards water and functional groups. Here we report on the synthesis of the novel tetrakis(pentafluoroethyl)indate, [In(C2 F5 )4 ]- , and its characterization in salts with the cations [Li(thf)3 ]+ , Cs+ , [PPh4 ]+ and [H14 O6 ]2+ (thf=tetrahydrofuran). To the best of our knowledge, these salts constitute the first perfluoroalkylindates and, in general, the first isolated perfluoroalkylindium compounds which are fully characterized by NMR spectroscopy, mass spectrometry, elemental analysis and X-ray diffraction analysis.

Ice nucleation in aqueous solutions of short- and long-chain poly(vinyl alcohol) studied with a droplet microfluidics setup.

Poly(vinyl alcohol) (PVA) has ice binding and ice nucleating properties. Here, we explore the dependence of the molecular size of PVA on its ice nucleation activity. For this purpose, we studied ice nucleation in aqueous solutions of PVA samples with molar masses ranging from 370 to 145 000 g mol-1, with a particular focus on oligomer samples with low molar mass. The experiments employed a novel microfluidic setup that is a follow-up on the previous WeIzmann Supercooled Droplets Observation on a Microarray (WISDOM) design by Reicher et al. The modified setup introduced and characterized here, termed nanoliter Bielefeld Ice Nucleation ARraY (nanoBINARY), uses droplet microfluidics with droplets (96 ± 4) µm in diameter and a fluorinated continuous oil phase and surfactant. A comparison of homogeneous and heterogeneous ice nucleation data obtained with nanoBINARY to those obtained with WISDOM shows very good agreement, underpinning its ability to study low-temperature ice nucleators as well as homogeneous ice nucleation due to the low background of impurities. The experiments on aqueous PVA solutions revealed that the ice nucleation activity of shorter PVA chains strongly decreases with a decrease in molar mass. While the cumulative number of ice nucleating sites per mass nm of polymers with different molar masses is the same, it becomes smaller for oligomers and completely vanishes for dimer and monomer representatives such as 1,3-butanediol, propan-2-ol, and ethanol, most likely because these molecules become too small to effectively stabilize the critical ice embryo. Overall, our results are consistent with PVA polymers and oligomers acting as heterogeneous ice nucleators.

Access to cyclopropanes with geminal trifluoromethyl and difluoromethylphosphonate groups.

A synthetic route to the bench-stable fluorinated masked carbene reagent diethyl 2-diazo-1,1,3,3,3-pentafluoropropylphosphonate, bearing a trifluoromethyl and a difluoromethyl group is reported for the first time. Its application in CuI-catalyzed cyclopropanation reactions with aromatic and aliphatic terminal alkenes under mild reaction conditions is demonstrated. In total, sixteen new cyclopropanes were synthesized in good to very good yields.

Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides.

Phosphoranides are interesting hypervalent species which serve as model compounds for intermediates or transition states in nucleophilic substitution reactions at trivalent phosphorus substrates. Herein, the syntheses and properties of stable trifluoromethylphosphoranide salts are reported. [K(18-crown-6)][P(CF3 )4 ], [K(18-crown-6)][P(CF3 )3 F], and [NMe4 ][P(CF3 )2 F2 ] were obtained by treatment of trivalent precursors with sources of CF3 - or F- units. These [P(CF3 )4-n Fn ]- (n=0-2) salts exhibit fluorinating (n=1-2) or trifluoromethylating (n=0) properties, which is disclosed by studying their reactivity towards selected electrophiles. The solid-state structures of [K(18-crown-6)][P(CF3 )4 ] and [K(18-crown-6)][P(CF3 )3 F] are ascertained by single crystal X-ray crystallography. The dynamics of these compounds are investigated by variable temperature NMR spectroscopy.

Free Difluorobis(pentafluoroethyl)phosphoranide Ion and Its Ligand Properties.

In this contribution, we report on the "free" [P(C2F5)2F2]- ion and its ligand properties in transition metal complex chemistry. For this purpose, Ag[P(C2F5)2F2] was treated with [{(Et2N)3P═N}3P═NHC(CH3)3]Cl ([EtP4H]Cl) to yield [EtP4H][P(C2F5)2F2], featuring a weakly coordinating phosphazenium cation. Due to the weak interaction between the cation and anion, the [P(C2F5)2F2]- ion meets the so-called pseudo-gas-phase conditions. To determine the Tolman electronic parameter, [EtP4H][Ni(CO)3{P(C2F5)2F2}] was prepared from [EtP4H][P(C2F5)2F2] and [Ni(CO)4], facilitating the classification of the P(C2F5)2F2 moiety as a moderately π-acidic ligand. By treatment of [EtP4H][P(C2F5)2F2] with [AuCl(tht)], the neutral tetrahydrothiophene ligand was substituted by the phosphoranide ion, yielding [EtP4H][AuCl{P(C2F5)2F2}]. When Ag[P(C2F5)2F2] was treated with [AuCl(tht)], on the other hand, the chloride was substituted. Transmetalation reactions of this type proved to be an efficient transfer method of the P(C2F5)2F2 moiety, as further demonstrated by the reactions of Ag[P(C2F5)2F2] with [FeCl(CO)2Cp], [FeCl(CO)2Cp*], and [PdCl2(NCMe)2]. Surprisingly, P(C2F5)2F demonstrated fluorinating abilities toward [FeCl(CO)2Cp], [FeCl(CO)2Cp*], [AuCl(tht)], and [PdCl2(NCMe)2]. Apparently, fluorido transition metal complexes were generated in situ under the formation of P(C2F5)2Cl. The fluorido iron and palladium complexes transfer their fluoride ions onto P(C2F5)2F, yielding the respective phosphoranido complexes, featuring the P(C2F5)2F2 moiety.

Oxidative Additions of C-F Bonds to the Silanide Anion [Si(C2 F5 )3 ].

Compounds exhibiting main group elements in low oxidation states were found to mimic the reactivity of transition metal complexes. Like the latter, such main group species show a proclivity of changing their oxidation state as well as their coordination number by +2, therefore fulfilling the requirements for oxidative additions. Prominent examples of such main group compounds that undergo oxidative additions with organohalides R-X (R=alkyl, aryl, X=F, Cl, Br, I) are carbenes and their higher congeners. Aluminyl anions, which like carbenes and silylenes oxidatively add to strong σ-bonds in R-X species, have been recently discovered. We present the first anion based upon a Group 14 element, namely the tris(pentafluoroethyl)silanide anion, [Si(C2 F5 )3 ]- , which is capable of oxidative additions towards C-F bonds. This enables the isolation of non-chelated tetraorganofluorosilicate salts, which to the best of our knowledge had only been observed as reactive intermediates before.

Tris(pentafluoroethyl)silanol Derivatives and the Lewis Amphoteric Tris(pentafluoroethyl)silanolate Anion, [Si(C2 F5 )3 O].

While alkyl-substituted siloxanes are widely known, virtually nothing is known about perfluoroalkyl siloxanes and their congener species, the silanols and silanolates. We recently reported on the tris(pentafluoroethyl)silanide ion, [Si(C2 F5 )3 ]- , which features Lewis amphoteric character deriving from the pentafluoroethyl substituents and their strong electron-withdrawing properties. Transferring this knowledge, we investigated the Lewis amphoteric behavior of the tris(pentafluoroethyl)silanolate, [Si(C2 F5 )3 O]- . In order to examine such Lewis amphoteric behavior, we first developed a strategy for the synthesis of the corresponding silanol Si(C2 F5 )3 OH, which readily condenses at room temperature to the hexakis(pentafluoroethyl)disiloxane, (C2 F5 )3 SiOSi(C2 F5 )3 . Deprotonation of Si(C2 F5 )3 OH employing a sterically demanding phosphazene base allows the characterization of the first example of a dimeric triorganosilanolate: the dianionic hexakis(pentafluoroethyl)disilanolate, [{Si(C2 F5 )3 O}2 ]2- , implies Lewis amphoteric character of the monomeric [Si(C2 F5 )3 O]- anion.

Difluorobis(pentafluoroethyl)phosphoranide: A Promising Building Block for Phosphoranidometal Complexes.

Despite the fact that different metal tetrafluorophosphoranides, M[PF4] (M = Cs, Ag, K), decompose readily, we successfully enhanced the stability of such species by the replacement of two fluorine atoms with electron withdrawing pentafluoroethyl groups. Thus, AgF adds to P(C2F5)2F, yielding Ag[P(C2F5)2F2], which served as a starting material for the synthesis of mono-, bis-, and tris[difluorobis(pentafluoroethyl)phosphoranido]silver complexes. Addition of 2,2'-bipyridine allowed for the isolation of stable [Ag(bipy){P(C2F5)2F2}], whereas the reaction with the chlorides [NMe4]Cl and CoCl2 afforded the bis- and trisphosphoranidoargentates [NMe4][Ag{P(C2F5)2F2}2(OEt2)] and [Co(NCMe)6][Ag{P(C2F5)2F2}3]·2MeCN, respectively. Altogether, the difluorobis(pentafluoroethyl)phosphoranido moiety serves as a novel, small, noncyclic phosphoranido ligand. It provided access to the first homoleptic phosphoranidometal complex, [Co(NCMe)6][Ag{P(C2F5)2F2}3]·2MeCN, which itself features the unusual structural motif of an [AgX3]2- ion.

Evidence of the Lewis-Amphoteric Character of Tris(pentafluoroethyl)silanide, [Si(C2 F5 )3 ].

According to a first view on the geometrical and electronic structure of the tris(pentafluoroethyl)silanide, this anion appears as a Lewis base. Quantum chemical calculations on perfluoroalkylated silanides show significantly lower HOMO and LUMO energy levels in comparison to their non-fluorinated counterparts, which implies reduced Lewis basicity and increased Lewis acidity of the [Si(C2 F5 )3 ]- ion. With these findings and a HOMO-LUMO gap of 4.80 eV similar to N-heterocyclic silylenes (NHSis), perfluoroalkyl silanides are predestined to exhibit Lewis-amphoteric character similar to silylenes. Deprotonation of Si(C2 F5 )3 H with sterically demanding phosphazene bases afforded thermally stable phosphazenium salts of the [Si(C2 F5 )3 ]- anion, which add to benzaldehyde, benzophenone, CS2 , and CO2 in various manners. This behavior also mirrors the reactivity of silylenes towards ketones as well as heterocumulenes and is rationalized by Lewis amphotericity being inherent in these silanides.

Triorganylphosphoranides: Realization of an Unusual Structural Motif Utilizing Electron Withdrawing Pentafluoroethyl Groups.

Phosphoranides comprising three phosphorus carbon bonds are scarcely represented in the literature. We now utilized tris(pentafluoroethyl)phosphane, P(C2 F5 )3 , and cyanobis(pentafluoroethyl)phosphane, P(C2 F5 )2 (CN), featuring electron withdrawing pentafluoroethyl groups, to synthesize such compounds. Metal fluorides MF (M=Ag, Cs) add to P(C2 F5 )3 yielding respective M[P(C2 F5 )3 F] salts. Those M[P(C2 F5 )3 F] subsequently suffer a loss of C2 F4 , furnishing M[P(C2 F5 )2 F2 ]. The cesium salt decomposes instantaneously when warmed to rt, whereas the silver salt decomposes slowly over several days at rt. Treatment of Ag[P(C2 F5 )3 F] with 2,2'-bipyridine facilitated the isolation and structural characterization of [Ag(bipy){P(C2 F5 )3 F}]. With P(C2 F5 )2 (CN), AgF reacts under substitution of the cyano group yielding P(C2 F5 )2 F, rather than phosphoranide formation. However, [K(18-crown-6)]F adds to P(C2 F5 )2 (CN) furnishing [K(18-crown-6)][P(C2 F5 )2 (CN)F]. Its structural characterization was successful, despite its tendency to undergo an exchange of substituents, yielding [K(18-crown-6)][P(C2 F5 )2 F2 ] and presumably [K(18-crown-6)][P(C2 F5 )2 (CN)2 ]. The latter forms an equilibrium with [K(18-crown-6)]CN and P(C2 F5 )2 (CN) which lies well on side of the phosphane and cyanide salt.

Ru-Catalyzed Hydrogen Atom Transfer/C-F Bond Cleavage of Difluoroalkyl Diazos with Hantzsch Ester via a Photocatalytic Radical Process.

A Ru-catalyzed reaction of difluoroalkyl diazo compounds with Hantzsch ester under visible light to achieve the formation of α-fluorovinylphosphonates via a radical process has been developed. Mechanistic experiments and density functional theory calculations reveal that the generation of a carbon radical is directly through the hydrogen atom transfer (HAT) by Hantzsch ester. This system represents the first example of generation of carbon radicals from diazo compounds via Hantzsch-ester-assisted HAT and also demonstrates a new radical-involved pathway for the difluoroalkyl diazo compounds.