Reaction of tetraphosphine platinum(II) complexes with 2-azidoethyl isocyanide 3 in methanol leads to complexes with two trans-coordinated NH,NH-stabilized carbene ligands 6(X)(2). Complexes 6(X)(2) react with phenyldivinylphosphine under substitution of the remaining phosphine ligands followed by an intramolecular hydroamination reaction to produce complex 1(PF(6))(2) with a macrocyclic [16]ane-P(2)C(NHC)(2) ligand.

Starting from complexes of type [Ru(Cp)Cl(P-P)] (P-P = 2PPh3, 3a; P-P = 2PMe3, 3b: P-P = dppe, 3c; P-P = dppp, 3d) isocyanide complexes [Ru(Cp)(P-P)(CNR) 4a-4d (CNR = CN-CH2-CH2N3, 1) and 7a-7d (CN-C6H4-2N3, 2) have been prepared. Reduction of the azido functions of the coordinated isocyanide ligands with Zn/NH4Cl/H2O in methanol leads to coordinated 2-amino functionalized isocyanides which cyclize to yield the complexes with a saturated NH,NH-stabilized NHC ligand 5a-5d or a benzannulated NH,NH-stabilized NHC ligand 8a-8d. The Zn/NH4Cl/H2O reduction method is of general applicability and allowed the generation of complex 11 bearing three saturated NH,NH-stabilized NHC ligands.

Reaction of [RuCl 2 (p-cymene)] 2 with 2-azidoethyl isocyanide (1a) or 2-azidophenyl isocyanide (1b) leads to the isocyanide complexes [RuCl 2 (p-cymene)(1a)] [2a] and [RuCl 2 (p-cymene)(1b)] [2b], respectively. Complex [2a] reacts with triphenylphosphine to yield the complex with a phosphiniminesubstituted isocyanide ligand [3]. The attempted hydrolysis of the phosphinimine group in [3] with HCl • Et 2 O produced the complex with a protonated phosphinimine ligand [4]Cl instead of the expected complex with a 2-aminoethyl isocyanide ligand. An alternative method for the reduction of the azido group in [2a] and [2b] using FeCl 3 /NaI has been applied leading to complexes with the 2-amino-substituted isocyanide ligands, which undergo intramolecular ring closure to yield the complexes of type [RuI 2 (pcymene)(NHC)], [5a] and [5b].

Complex [Fe(η5‐C5H5)(η6‐PhMe)]PF6 reacts with 1,2‐bis[bis(2‐fluorophenyl)phosphanyl]benzene (2) in acetonitrile under irradiation for 6 h to give complex [Fe(η5‐C5H5)(2)(CH3CN)]PF6 ([3]PF6). Reaction of [3]PF6 with 1 equiv. of 2‐azidoethyl isocyanide (4) yields complex [Fe(η5‐C5H5)(2)(4)]X ([5]X) (X = Br, PF6). Staudinger reaction with PPh3 at the azido function followed by hydrolysis of the iminophosphorane with HBr yields compound [6]X (X = Br–, PF6 –) with an NH,NH‐stabilized NHC ligand. The facially coordinated NH,NH‐stabilized NHC and the fluorinated diphosphane ligands were linked by N,N′‐deprotonation of the NHC and nucleophilic attack of the nitrogen atoms at two C–F bonds, which gave – after anion exchange with NH4PF6 – complex [1]PF6 bearing the macrocyclic [11]ane‐P2CNHC ligand.

quais mostram diferentes graus de impedimento estérico na posição 2, foram preparados a partir dos correspondentes fenóis. Uma despronotação inicial dos fenóis foi obtida com o uso de NaH em dimetoxietano, seguido de tratamento com cloreto de N,N-dimetiltiocarbomoila, obtendo-se os O-ariltiocarbamatos. A termólise destes compostos resultou num rearranjo, obtendo-se os S-ariltiocarbamatos. Finalmente, a redução dos Sariltiocarbamatos com LiAlH 4 em THF, seguido de acidificação, levou ao isolamento dos tiofenóis. Todos os produtos foram caracterizados por técnicas espectroscópicas, e para alguns tiocarbamatos a estrutura sólida foi determinada por difração de raio X.A series of thiophenols with different ortho-substituents, 2,4-dimethylthiophenol, 2-tert-butyl-4-methylthiophenol, and 2-(1-adamantyl)-4-methylthiophenol, which display varying degrees of steric hindrance on the 2-position, was prepared from the corresponding phenols. Initial deprotonation of the phenols was achieved with NaH in dimethoxyethane, followed by treatment with N,Ndimethylthiocarbamoyl chloride, to obtain the O-arylthiocarbamates. Thermolysis of the latter compounds resulted in rearrangement, which yields the desired S-arylthiocarbamates. Finally, reduction of the S-arylthiocarbamates with LiAlH 4 in THF, followed by acidic workup, allowed the isolation of the thiophenols. All products were characterized by spectroscopic techniques, and in the case of some of the thiocarbamates the solid state structures were determined by single-crystal X-ray diffraction.

Reaction of [RuCl(Cp)(PPh 3 ) 2 ] with bis[di(2-fluorophenyl)phosphino]benzene, 3, yields complex [RuCl(Cp)(3)], [4]. The chloro ligand in [4] can be exchanged for the 2-azidoethyl isocyanide ligand 2, giving complex [Ru(Cp)(2)(3)]Cl, [5]Cl, which reacts with NH 4 BF 4 to give [5]BF 4 . The azido group of the coordinated isocyanide ligand in [5]Cl or [5]BF 4 can be reduced with Zn/NH 4 Cl/H 2 O to give the complex with the 2-aminoethyl isocyanide ligand. This ligand is not stable but cyclizes by an intramolecular nucleophilic attack of the amino group at the isocyanide carbon atom to give an NH, NH-stabilized NHC ligand in complexes [6]X (X = Cl, [6]Cl; X = 0.5 ZnCl 4 , [6] 2 (ZnCl 4 ); X = BF 4 , [6]BF 4 ). Deprotonation of the NH,NH-stabilized NHC ligands in cations of type [6] þ leads to an intramolecular nucleophilic attack of the amido nitrogen atoms at the fluorinated phenyl groups of the diphosphine ligand under formation of the complex with the facially coordinated macrocyclic [11]ane-P 2 C NHC ligand [1]X (X = Cl, [1]Cl; X = 0.5 ZnCl 4 , [1] 2 (ZnCl 4 ); X = BF 4 , [1]BF 4 ). Formation of the macrocycle is facilitated by the steric pressure excerted by the cyclopentadienyl ligand. The molecular structures of [4], [5]BF 4 , [6]BF 4 3 CH 2 Cl 2 , and [1]Cl 3 CH 2 Cl 2 3 0.5H 2 O have been determined by X-ray diffraction.

Reaction of 2 equiv of 2-azidoethyl isocyanide and the tetraphosphine platinum(II) complexes [1a−c](X) 2 (a, PR 3 = PMe 3 ; b, PR 3 = PMe 2 Ph; c, PR 3 = PMePh 2 ) yielded via phosphine substitution and template-controlled cyclization of the isocyanide ligands the trans-di(NH,NH-NHC) complexes [2a−c](X) 2 . Treatment of [2c](PF 6 ) 2 with an additional 2 equiv of 2-azidoethyl isocyanide gave the tetracarbene complex [3](PF 6 ) 2 , bearing four protic NH,NH-NHC ligands derived from a five-membered heterocycle. The same template synthesis utilizing 3-azidopropyl isocyanide and complex [1c](PF 6 ) 2 gave the dicarbene complex [5](PF 6 ) 2 and, after addition of 2 equiv more of 3-azidopropyl isocyanide, the tetracarbene complex [6](PF 6 ) 2 with four protic NH,NH-NHC ligands derived from a six-membered heterocycle. The intermediate trans-di(NH,NH-NHC) platinum(II) complex [5](PF 6 ) 2 also reacts with 2 equiv of 2-azidoethyl isocyanide to give the tetracarbene complex [7](PF 6 ) 2 , bearing two five-membered-ring NHCs and two six-membered-ring NHCs.

A neutral aminotrithioether interacts with CuI, generating a coordination polymer in the solid state. Electrochemical studies indicate that the ligand is prone to oxidation by CuII, which results in a novel C-C bond formation reaction.