Palladium Terminal Imido Complexes with Nitrene Character.

Whereas triplet-nitrene complexes of the late transition metals are isolable and key intermediates in catalysis, singlet-nitrene ligands remain elusive. Herein we communicate three such palladium terminal imido complexes with singlet ground states. UV-vis-NIR electronic spectroscopy with broad bands up to 1400 nm as well as high-level computations (DFT, STEOM-CCSD, CASSCF/NEVPT2, EOS analysis) and reactivity studies suggest significant palladium(0) singlet-nitrene character.

Thermally Activated Delayed Fluorescence and Phosphorescence Quenching in Iminophosphonamide Copper and Zinc Complexes.

The synthesis of copper and zinc complexes of four variably substituted iminophosphonamide ligands is presented. While the copper complexes form ligand-bridged dimers, the zinc compounds are monomeric. Due to different steric demand of the ligand the arrangement of the ligands within the dimeric complexes varies.

Enantiopure Calcium Iminophosphonamide Complexes: Synthesis, Photoluminescence, and Catalysis.

The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L-H (L=[Ph P{N(R)CH(CH )Ph} ]), L'-H (L'=[Ph P{NDipp}{N(R)CH(CH )Ph}]), (Dipp=2,6- Pr C H ), and L''-H (L''=[Ph P{N(R)CH(CH )naph} ]), (naph=naphthyl) is presented. The resulting structures [L Ca], [L' Ca], and [L'' Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue-green photoluminescence (PL) in the solid state, which is especially bright at low temperatures.

A bis(germylene) functionalized metal-coordinated polyphosphide and its isomerization.

Pentaphosphaferrocene, [Cp*Fe(η5-P5)] (Cp* = η5-C5Me5), was used as a polyphosphorus source to obtain germylene-polyphosphide complexes. A stepwise reactivity was observed between the di-germylene, [LGe-GeL] (L = {PhC(NtBu)2}), and [Cp*Fe(η5-P5)]. Firstly, reductive homolytic cleavage of the Ge-Ge single bond in [LGe-GeL] led to [(LGe)2{(μ,η4-P5)FeCp*}].

Regioselective Insertion of Aluminum(I) in the cyclo-P Ring of Pentaphosphaferrocene.

A route to directly access mixed Al-Fe polyphosphide complexes was developed. The reactivity of pentaphosphaferrocene, [Cp*Fe(η -P )] (Cp*=C Me ), with two different low-valent aluminum compounds was investigated. The steric and electronic environment around the [Al ] centre are found to be crucial for the formation of the resulting Al-Fe polyphosphides.

Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal-Coordinated Polyphosphide.

Selective substitution and insertion reactions of silylenes into the P ring of [Cp*Fe(η-P)] are reported. The selective substitution of one P atom by an isoelectronic [Si] fragment ( = PhC(NBu)) leads to [(η-PSi)FeCp*] and [Si(Cl)═P-Si(Cl)]. To elucidate the reaction mechanism, [{Si(N(SiMe))}{(η-P)FeCp*}], in which the silicon atom binds to the P ring, was synthesized as a model compound for the reaction intermediate.

Neutral and cationic enantiopure group 13 iminophosphonamide complexes.

Synthesis and reactivity of enantiopure iminophosphonamide ligand L-H (L = [Ph2P{N(R)CH(CH3)Ph}2]) with group 13 metal compounds has been investigated. The reaction of L-H with LiAlH4 afforded the aluminium monohydride complex [L2AlH]. The monochloride complexes [L2MCl] (M = Al, Ga) were accessed by reacting corresponding MCl3 (M = Al, Ga) with L-Li.

Alkali metal complexes of an enantiopure iminophosphonamide ligand with bright delayed fluorescence.

The enantiomerically pure ligand ,-diphenyl-,'-bis(()-1-phenylethyl)phosphinimidic amide (; (R)-HPEPIA) was synthesized and subsequently deprotonated with alkali metal precursors to yield dimeric complexes [M{(R)-PEPIA}] (M = Li (), Na (), K (), Rb ()). The cesium compound [M{(R)-PEPIA}] () crystallized as a cocrystal composed of dimeric ([Cs{(R)-PEPIA}] ( ) and 1D-polymeric ([Cs{(R)-PEPIA}] ) ( ) species in a 1 : 1 ratio. The coordination polymer features a unique sinus-shaped configuration of repeating -Cs-N-P-N-Cs-N-P-N- units.

Neutral and cationic cyclic (alkyl)(amino)carbene mercury [cAAC-Hg(ii)] complexes: scope of hydroamination of alkynes with organomercury compounds.

This study demonstrates the first synthesis of cyclic (alkyl)(amino)carbene (cAAC) adducts of Hg(ii), [cAACMe·HgBr(μ-Br)]2 (1a) and [cAACcy·HgBr(μ-Br)]2 (1b). Adduct 1b catalyzes intermolecular hydroamination of aromatic alkynes and amines under mild conditions to afford aromatic imines. The quest to prepare an electrophilic Hg(ii) complex resulted in the synthesis of cationic [(cAACcy)2Hg(H2O)]2+2[NO3]- (3) by reacting 1b with AgNO3.