Coordination Chemistry of P4 S3 and P4 Se3 towards the Iron Fragments [Fe(Cp)(CO)2 ]+ and [Fe(Cp)(PPh3 )(CO)].

The complexes Ag(L)n [WCA] (L=P4 S3 , P4 Se3 , As4 S3 , and As4 S4 ; [WCA]=[Al(ORF )4 ]- and [F{Al(ORF )3 }2 ]- ; RF =C(CF3 )3 ; WCA=weakly coordinating anion) were tested for their performance as ligand-transfer reagents to transfer the poorly soluble nortricyclane cages P4 S3 , P4 Se3 , and As4 S3 as well as realgar As4 S4 to different transition-metal fragments. As4 S4 and As4 S3 with the poorest solubility did not yield complexes. However, the more soluble silver-coordinated P4 S3 and P4 Se3 cages were transferred to the electron-poor Fp+ moiety ([CpFe(CO)2 ]+ ). Thus, reaction of the silver salt in the presence of the ligand with Fp-Br yielded [Fp-P4 S3 ][Al(ORF )4 ] (1 a), [Fp-P4 S3 ][F(Al(ORF )3 )2 ] (1 b), and [Fp-P4 Se3 ][Al(ORF )4 ] (2). Reactions with P4 S3 also yielded [FpPPh3 -P4 S3 ][Al(ORF )4 ] (3), a complex with the more electron-rich monophosphine-substituted Fp+ analogue [FpPPh3 ]+ ([CpFe(PPh3 )(CO)]+ ). All complex salts were characterized by single-crystal XRD, NMR, Raman, and IR spectroscopy. Interestingly, they show characteristic blueshifts of the vibrational modes of the cage, as well as structural contractions of the cages upon coordination to the Fp/FpPPh3 moieties, which oppose the typically observed cage expansions that lead to redshifts in the spectra. Structure, bonding, and thermodynamics were investigated by DFT calculations, which support the observed cage contractions. Its reason is assigned to σ and π donation from the slightly P-P and P-E antibonding P4 E3 -cage HOMO (e symmetry) to the metal acceptor fragment.

From Phosphidic to Phosphonium? Umpolung of the P4 -Bonding Situation in [CpFe(CO)(L)(η1 -P4 )]+ Cations (L=CO or PPh3 ).

Upon coordinating P4 to electron poor cyclopentadienyl-iron cations, the average P-P bond distances shrink and the respective P4 breathing mode in the Raman spectra (600 cm-1 , P4, free ) is blueshifted by >40 cm-1 in [CpFe(CO)(L)(η1 -P4 )]+ cations (L=CO or PPh3 ). Analysis suggests that this corresponds to an umpolung of the bonding from more phosphidic in the known, electron-rich systems to more phosphonium-like in the reported electron-poor versions. This may open new functionalization pathways for white phosphorus P4 .

First experimental evidence for the elusive tetrahedral cations [EP3]+ (E = S, Se, Te) in the condensed phase.

Condensed phase access to the unprecedented tetrahedral cations [EP3]+ (E = S, Se, Te) was achieved through the reaction of ECl3[WCA] with white phosphorus ([WCA]- = [Al(ORF)4]- and [F(Al(ORF)3)2]-; -RF = -C(CF3)3). Previously, [EP3]+ was only known from gas phase MS investigations. By contrast, the reaction of ECl3[A] with the known P3 3- synthon Na[Nb(ODipp)3(P3)] (enabling AsP3 synthesis), led to formation of P4. The cations [EP3]+ were characterized by multinuclear NMR spectroscopy in combination with high-level quantum chemical calculations. Their bonding situation is described with several approaches including Atoms in Molecules and Natural Bond Orbital analysis. The first series of well-soluble salts ECl3[WCA] was synthesized and fully characterized as starting materials for the studies on this elusive class of [EP3]+ cations. Yet, with high [ECl3]+ fluoride ion affinity values between 775 (S), 803 (Se) and 844 (Te) kJ mol-1, well exceeding typical phosphenium ions, these well-soluble ECl3[WCA] salts could be relevant in view of the renewed interest in strong (also cationic) Lewis acids.

Facile and systematic access to the least-coordinating WCA [(RFO)3Al-F-Al(ORF)3]- and its more Lewis-basic brother [F-Al(ORF)3]- (RF = C(CF3)3).

By reaction of the Lewis acid Me3Si-F-Al(ORF)3 with a series of [PF6]- salts, gaseous PF5 and Me3Si-F are liberated and salts of the anion [F-Al(ORF)3]- ([f-al]-; RF = C(CF3)3) can be obtained. By addition of another equivalent of Me3Si-F-Al(ORF)3 to [f-al]-, gaseous Me3Si-F is released and salts of the least coordinating anion [(RFO)3Al-F-Al(ORF)3]- ([al-f-al]-) are formed. Both procedures work for a series of synthetically useful cations including Ag+, [NO]+, [Ph3C]+ and in very clean reactions with 5 g batch sizes giving excellent yields typically exceeding 90%. In addition, the synthesis of Me3Si-F-Al(ORF)3 has been optimized and scaled up to 85 g batches in an one-pot procedure. These anions could previously only be obtained by difficult to control decomposition reactions of [Al(ORF)4]- or by halide abstraction reactions with Me3Si-F-Al(ORF)3, generating relatively large countercations that are unsuited for further use as universal starting materials. Especially [al-f-al]- is of interest for the stabilization of reactive cations, since it is even weaker coordinating than [Al(ORF)4]- and more stable against strong electrophiles. This bridged anion can be seen as an adduct of [f-al]- and Al(ORF)3. Thus, it is similarly Lewis acidic as BF3 and eventually reacts with nucleophiles (Nu) from the reaction environment to yield Nu-Al(ORF)3 and [f-al]-. This prevents working with [al-f-al]- salts in ethereal or other donor solvents. By contrast, the [f-al]- anion is no longer Lewis acidic and may therefore be used for reactions involving stronger nucleophiles than the [al-f-al]- anion can withstand. Subsequently it may be transformed into the [al-f-al]- salt by simple addition of one equivalent of Me3Si-F-Al(ORF)3.

Synthesis, Characterisation and Reactions of Truly Cationic NiI -Phosphine Complexes.

The recently published purely metallo-organic NiI salt [Ni(cod)2 ][Al(ORF )4 ] (1, cod=1,5-cyclooctadiene, RF =C(CF3 )3 ) provides a starting point for a new synthesis strategy leading to NiI phosphine complexes, replacing cod ligands by phosphines. Clearly visible colour changes indicate reactions within minutes, while quantum chemical calculations (PBE0-D3(BJ)/def2-TZVPP) approve exergonic reaction enthalpies in all performed ligand exchange reactions. Hence, [Ni(dppp)2 ][Al(ORF )4 ] (2, dppp=1,3-bis(diphenylphosphino)propane), [Ni(dppe)2 ][Al(ORF )4 ] (3, dppe=1,3-bis(diphenyl-phosphino)ethane), three-coordinate [Ni(PPh3 )3 ][Al(ORF )4 ] (4) and a remarkable two-coordinate NiI phosphine complex [Ni(PtBu3 )2 ][Al(ORF )4 ] (5) were characterised by single crystal X-ray structure analysis. EPR studies were performed, confirming a nickel d9 -configuration in complexes 2, 4 and 5. This result is supported by additional magnetization measurements of 4 and 5. Further investigations by cyclic voltammetry indicate relatively high oxidation potentials for these NiI compounds between 0.7 and 1.7 V versus Fc/Fc+ . Screening reactions with O2 and CO gave first insights on the reaction behaviour of the NiI phosphine complexes towards small molecules with formation of mixed phosphine-CO-NiI complexes and oxidation processes yielding new NiI and/or NiII derivatives. Moreover, 4 reacted with CH2 Cl2 at RT to give a dimeric NiII ylide complex (4 c). As CH2 Cl2 is a rather stable alkyl halide with relatively high C-Cl bond energies, 4 appears to be a suitable reagent for more general C-Cl bond activation reactions.

[Ni(cod)2][Al(OR(F))4], a Source for Naked Nickel(I) Chemistry.

The straightforward synthesis of the cationic, purely organometallic Ni(I) salt [Ni(cod)2](+)[Al(OR(F))4](-) was realized through a reaction between [Ni(cod)2] and Ag[Al(OR(F))4] (cod = 1,5-cyclooctadiene). Crystal-structure analysis and EPR, XANES, and cyclic voltammetry studies confirmed the presence of a homoleptic Ni(I) olefin complex. Weak interactions between the metal center, the ligands, and the anion provide a good starting material for further cationic Ni(I) complexes.