Functionalization of Tetraphosphido Ligands by Heterocumulenes.

Although numerous polyphosphido complexes have been accessed through the transition-metal-mediated activation and functionalization of white phosphorus (P4), the selective functionalization of the resulting polyphosphorus ligands in these compounds remains underdeveloped. In this study, we explore the reactions between cyclotetraphosphido cobalt complexes and heterocumulenes, leading to functionalized P4 ligands. Specifically, the reaction of carbon disulfide (CS2) with [K(18c-6)][(Ar*BIAN)Co(η4-P4)] ([K(18c-6)]1, 18c-6 = [18]crown-6) affords the adduct [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4CS2)] ([K(18c-6)]3), in which CS2 is attached to a single phosphorus atom (Ar* = 2,6-dibenzhydryl-4-isopropylphenyl, BIAN = 1,2-bis(arylimino)acenaphthene diimine). In contrast, the insertion of bis(trimethylsilyl)sulfur diimide S(NSiMe3)2 into a P-P bond of [K(18c-6)]1 yields [K(18c-6)][(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)2)] (K(18c-6)]4). This salt further reacts with Me3SiCl to form [(Ar*BIAN)Co(η3:η1-P4SN2(SiMe3)3] (5), featuring a rare azatetraphosphole ligand. Moreover, treatment of the previously reported complex [(Ar*BIAN)Co(η3:η1-P4C(O)tBu)] (2) with isothiocyanates results in P-C bond insertion, yielding [(Ar*BIAN)Co(η3:η1-P4C(S)N(R)C(O)tBu)] (6a,b; R = Cy, Ph).

Low-Valent Transition Metalate Anions in Synthesis, Small Molecule Activation, and Catalysis.

This review surveys the synthesis and reactivity of low-oxidation state metalate anions of the d-block elements, with an emphasis on contributions reported between 2006 and 2022. Although the field has a long and rich history, the chemistry of transition metalate anions has been greatly enhanced in the last 15 years by the application of advanced concepts in complex synthesis and ligand design. In recent years, the potential of highly reactive metalate complexes in the fields of small molecule activation and homogeneous catalysis has become increasingly evident. Consequently, exciting applications in small molecule activation have been developed, including in catalytic transformations. This article intends to guide the reader through the fascinating world of low-valent transition metalates. The first part of the review describes the synthesis and reactivity of d-block metalates stabilized by an assortment of ligand frameworks, including carbonyls, isocyanides, alkenes and polyarenes, phosphines and phosphorus heterocycles, amides, and redox-active nitrogen-based ligands. Thereby, the reader will be familiarized with the impact of different ligand types on the physical and chemical properties of metalates. In addition, ion-pairing interactions and metal-metal bonding may have a dramatic influence on metalate structures and reactivities. The complex ramifications of these effects are examined in a separate section. The second part of the review is devoted to the reactivity of the metalates toward small inorganic molecules such as H2, N2, CO, CO2, P4 and related species. It is shown that the use of highly electron-rich and reactive metalates in small molecule activation translates into impressive catalytic properties in the hydrogenation of organic molecules and the reduction of N2, CO, and CO2. The results discussed in this review illustrate that the potential of transition metalate anions is increasingly being tapped for challenging catalytic processes with relevance to organic synthesis and energy conversion. Therefore, it is hoped that this review will serve as a useful resource to inspire further developments in this dynamic research field.

Cobalt-Mediated [3+1] Fragmentation of White Phosphorus: Access to Acylcyanophosphanides.

Despite the accessibility of numerous transition metal polyphosphido complexes through transition-metal-mediated activation of white phosphorus, the targeted functionalization of Pn ligands to obtain functional monophosphorus species remains challenging. In this study, we introduce a new [3+1] fragmentation procedure for cyclo-P4 ligands, leading to the discovery of acylcyanophosphanides and -phosphines. Treatment of the complex [K(18c-6)][(Ar*BIAN)Co(η4 -P4 )] ([K(18c-6)]3, 18c-6=[18]crown-6, Ar*=2,6-dibenzhydryl-4-isopropylphenyl, BIAN=1,2-bis(arylimino)acenaphthene diimine) with acyl chlorides results in the formation of acylated tetraphosphido complexes [(Ar*BIAN)Co(η4 -P4 C(O)R)] (R=tBu, Cy, 1-Ad, Ph; 4 a-d). Subsequent reactions of 4 a-d with cyanide salts yield acylated cyanophosphanides [RC(O)PCN]- (9 a-d- ) and the cyclo-P3 cobaltate anion [(Ar*BIAN)Co(η3 -P3 )(CN)]- (8- ). Further reactions of 4 a-d with trimethylsilyl cyanide (Me3 SiCN) and isocyanides provide insight into a plausible mechanism of this [3+1] fragmentation reaction, as these reagents partially displace the P4 C(O)R ligand from the cobalt center. Several potential intermediates of the [3+1] fragmentation were characterized. Additionally, the introduction of a second acyl substituent was achieved by treating [K(18c-6)]9b with CyC(O)Cl, resulting in the first bis(acyl)monocyanophosphine (CyC(O))2 PCN (10).

Counterion Effect in Cobaltate-Catalyzed Alkene Hydrogenation.

We show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation of the catalytic properties of [Cat][Co(η4 -cod)2 ] (Cat=K (1), Na (2), Li (3), (Dep nacnac)Mg (4), and N(n Bu)4 (5); cod=1,5-cyclooctadiene, Dep nacnac={2,6-Et2 C6 H3 NC(CH3 )}2 CH)]) demonstrated that the lithium salt 3 and magnesium salt 4 drastically outperform the other catalysts. Complex 4 was the most active catalyst, which readily promotes the hydrogenation of highly congested alkenes under mild conditions. A plausible catalytic mechanism is proposed based on density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation and DFT studies were used to examine the turnover-limiting migratory insertion step. The results of these studies suggest an active co-catalytic role of the counterion in the hydrogenation reaction through the coordination to cobalt hydride intermediates.

Selective hydroboration of electron-rich isocyanates by an NHC-copper(I) alkoxide.

The (IPr)CuOtBu catalysed reduction of 11 aryl and alkyl isocyanates with pinacolborane gave only the boraformamides, pinBN(R)C(O)H, in most cases. Overreduction, which hampers almost all isocyanate hydroborations, was restricted to electron poor aryl isocyanates (4-NC-C6H4NCO, 4-F3C-C6H4NCO, 3-O2N-C6H4NCO). Computational analysis showed stability of [(IPr)CuH]2, which was proposed to be the catalyst resting state, drives selectivity, suggesting an approach to prevent overreduction in future work. In the case of iPrNCO, formation of this species renders overreduction kinetically inaccessible. For 4-NC-C6H4NCO, however, the barrier height for the first step of over-reduction is much lower, even relative to [(IPr)CuH]2, resulting in unselective reduction.

A stable ring-expanded NHC-supported copper boryl and its reactivity towards heterocumulenes.

Reaction of bis(pinacolato)diboron with (6-Dipp)CuOtBu generates a ring-expanded N-heterocyclic carbene supported copper(I) boryl, (6-Dipp)CuBpin. This compound showed remarkable stability and was characterised by NMR spectroscopy and X-ray crystallography. (6-Dipp)CuBpin readily dechalcogenated a range of heterocumulenes such as CO2, isocyanates and isothiocyanates to yield (6-Dipp)CuXBpin (X = O, S). In the case of CO2 catalytic reduction to CO is viable in the presence of excess bis(pinacolato)diboron. In contrast, in the case of iso(thio)cyanates, the isocyanide byproduct of dechalcogenation reacted with (6-Dipp)CuBpin to generate a copper(I) borylimidinate, (6-Dipp)CuC(NR)Bpin, which went on to react with heterocumulenes. This off-cycle reactivity gives selective access to a range of novel boron-containing heterocycles bonded to copper, but precludes catalytic reactivity.

The first ring-expanded NHC-copper(i) phosphides as catalysts in the highly selective hydrophosphination of isocyanates.

A range of N-heterocyclic carbene-supported copper diphenylphosphides (NHC = IPr, 6-Dipp, SIMes and 6-Mes) were synthesised. These include the first reports of ring-expanded NHC-copper(i) phosphides. The compounds were characterised by NMR spectroscopy and X-ray crystallography. Reaction of (6-Dipp)CuPPh2 with isocyanates, isothiocyanates and carbon disulfide results in the insertion of the heterocumulene into the Cu-P bond. The NHC-copper phosphides were found to be the most selective catalysts yet reported for the hydrophosphination of isocyanates. They provide access to a broad range of phosphinocarboxamides in excellent conversion and good yield.