Alpha-metalated N,N-dimethylbenzylamine rare-earth metal complexes and their catalytic applications.

This perspective summarizes our group's extensive research in the realm of organometallic lanthanide complexes, while also placing the catalytic reactions supported by these species within the context of known lanthanide catalysis worldwide, with a specific focus on phosphorus-based catalytic reactions such as intermolecular hydrophosphination and hydrophosphinylation. α-Metalated N,N-dimethylbenzylamine ligands have been utilized to generate homoleptic lanthanide complexes, which have subsequently proven to be highly active lanthanum-based catalysts. The main goal of our research program has been to enhance the catalytic efficiency of lanthanum-based complexes, which began with initial successes in the stoichiometric synthesis of organometallic lanthanide complexes and utilization of these species in catalytic hydrophosphination reactions. Not only have these species supported traditional lanthanide catalysis, such as the hydrophosphination of heterocumulenes like carbodiimides, isocyanates, and isothiocyanates, but they have also been effective for a plethora of catalytic reactions tested thus far, including the hydrophosphinylation and hydrophosphorylation of nitriles, hydrophosphination and hydrophosphinylation of alkynes and alkenes, and the heterodehydrocoupling of silanes and amines. Each of these catalytic transformations is meritorious in its own right, offering new synthetic routes to generate organic scaffolds with enhanced functionality while concurrently minimizing both waste generation and energy consumption. Objectives: We aim for the research summary presented herein to inspire and encourage other researchers to investigate f-element based stoichiometric and catalytic reactions. Our efforts in this field began with the recognition that potassium salts of benzyldimethylamine preferred deprotonation at the α-position, rather than the ortho-position, and we wondered if this regiochemistry would be retained in the formation of lanthanide complexes. The pursuit of this simple idea led first to a series of structurally fascinating homoleptic organometallic lanthanide complexes with surprisingly good stability. Fundamental studies of the protonolysis chemistry of these complexes ultimately revealed highly versatile lanthanide-based precatalysts that have propelled a catalytic investigation spanning more than a decade. We anticipate that this summative perspective will animate the synthetic as well as biological communities to consider La(DMBA)3-based catalytic methods in the synthesis of functionalized organic scaffolds as an atom-economic, convenient, and efficient methodology. Ultimately, we envision our work making a positive impact on the advancement of novel chemical transformations and contributing to progress in various fields of science and technology.

Double Hydrophosphorylation of Nitriles Catalyzed by Rare-Earth-Metal Lanthanum.

A high-yielding and atom-efficient protocol for the double hydrophosphorylation of nitriles using a lanthanum-based N,N-dimethylbenzylamine complex (La(DMBA)3) as a precatalyst is reported. This method provides a straightforward and convenient approach for the synthesis of biologically important organophosphorus compounds known as N-(α-phosphoryl)amidophosphates in good to excellent yields. Nitriles with a broad range of additional functionality were tolerated, including those with halides, ethers, amines, and pyridyl groups.

Selective hydrosilylation of alkynes and ketones: contrasting reactivity between cationic 3-iminophosphine palladium and nickel complexes.

The catalytic hydrosilylation of alkynes and ketones has been explored utilizing palladium- and nickel(allyl) complexes supported by 3-iminophosphine ligands. Palladium and nickel demonstrated distinctly different reactivity profiles, with palladium proving very effective for the hydrosilylation of electron-deficient alkynes, while nickel excelled with ketones and internal alkynes. Additionally, in many cases, regioselective hydrosilylation was observed.

Cationic [(Iminophosphine)Nickel(Allyl)]+ Complexes as the First Example of Nickel Catalysts for Direct Hydroamination of Allenes.

The first example of nickel-catalyzed hydroamination of allenes is reported. The new cationic [(3-iminophosphine)nickel(allyl)]+ catalysts have been fully characterized and act regioselectively in the catalytic hydroamination of allenes with secondary amines at room temperature.

Highly efficient regioselective hydrosilylation of allenes using a [(3IP)Pd(allyl)]OTf catalyst; first example of allene hydrosilylation with phenyl- and diphenylsilane.

A [(3IP)Pd(allyl)]OTf complex was shown to function efficiently and regioselectively in allene hydrosilylation with phenyl- and diphenylsilane. The catalyst also proved to be highly active for allene hydrosilylation employing a wide range of silanes, each of which produced a single regioisomer.

Isolation and characterization of main group and late transition metal complexes using orthometallated imine ligands.

Several late transition metal and main group orthometallated imine complexes were synthesized by utilizing ortholithiated imine precursors. Magnesium, aluminum, zinc, copper(I), and tin(IV) complexes were isolated and characterized. Subsequent reactions with electrophiles such as Ph(2)PCl, MeI and I(2) yielded several functionalized products, including a new iminophosphine ligand and its corresponding copper(I) complex. The coordination modes of the orthometallated imine ligands, as well as the structures of the metal complexes, were studied in the solid state using small molecule X-ray diffraction when possible.

Mono-anionic acetophenone imine ligands: synthesis, ortho-lithiation and first examples of group (V) metal complexes.

A series of niobium and tantalum imido complexes with mono-anionic ortho-metallated acetophenone imine ligands have been prepared and characterized using NMR spectroscopy, mass spectrometry and elemental analysis. These low symmetry complexes are produced with only one or two structural isomers in all cases and display interesting correlations between the steric bulk of the ligands employed and the isomers formed. Crystal structures of several new niobium and tantalum complexes are presented as confirmation of the connectivity in these structural isomers.

Titanium imido complexes utilizing orthometallated derivatized acetophenone and piperonal imine ligands: synthesis, isolation, and characterization.

A series of five ortho-lithiated imines (Li-L(n); n = 1-5) was synthesized via the reaction of an aryl or alkyl acetophenone imine with n-butyllithium. The ortho-lithiated imines were subsequently reacted with Ti(NR)Cl(2)py(3) (R = C(CH(3))(3), 2,6-Me(2)C(6)H(3), 2,6-Et(2)C(6)H(3), or 2,6-(i)Pr(2)C(6)H(3)), yielding complexes of the form (L(n))(2)Ti(NR). Several of the resulting complexes [(L(1))(2)Ti(NC(CH(3))(3)), 1a; (L(3))(2)Ti(N-2,6-Me(2)C(6)H(3)), 3b; and (L(5))(2)Ti(NC(CH(3))(3)), 5a] were structurally characterized using small molecule X-ray diffraction. The C(2) symmetric complexes produced in these reactions displayed a distorted square pyramidal geometry. In each complex the titanium center was located above the square plane of the two coordinated bidentate ligands and the chelating C approximately N ligands were folded away from the metal center. When a less sterically demanding alkylimine was used (L(4)), the resulting complex was isolated as an equilibrium mixture of cis and trans isomers of the empirical formula (L(4))(2)Ti(NC(CH(3))(3))py (cis/trans 4a).

A versatile methodology for the synthesis of alpha,beta-unsaturated 3-iminophosphines.

Phorteen phine phosphines: Fourteen new alpha,beta-unsaturated beta-chloroimines were synthesized from inexpensive ketones by using the Vilsmeier-Haack reagent followed by Schiff-base condensation. Each imine was subsequently converted to an alpha,beta-unsaturated 3-iminophosphine through either late-metal-catalyzed phosphorus-carbon cross-coupling or through an addition-elimination sequence (see scheme). This high-yield protocol serves as a general means to produce alpha,beta-unsaturated 3-iminophosphines.Fourteen new alpha,beta-unsaturated beta-chloroimines were synthesized from commercially available ketones using the Vilsmeier-Haack reagent, followed by Schiff-base condensation. Each imine was subsequently converted to an alpha,beta-unsaturated 3-iminophosphine through either late-metal-catalyzed phosphorus-carbon cross-coupling or through an addition-elimination sequence. Depending on the substituents present on the vinyl group, the resultant phosphines were isolated as either E or Z diastereomers with successful isolation of predominately single diastereomers for all fourteen new phosphines investigated. Full synthetic and spectroscopic details, as well as several X-ray crystal structures of these new imines and phosphines, are reported in addition to X-ray crystal structures of related palladium complexes.

Neutral and Cationic Alkyl Tantalum Imido Complexes: Synthesis and Migratory Insertion Reactions.

The synthesis and reactivity of dibenzyl cationic tantalum imido complexes is described. The trialkyl tantalum imido compounds Bn(3)Ta=NCMe(3) (1) and Np(3)Ta=NCMe(3) (2) were synthesized as starting materials for the study of dialkyl cationic tantalum imido complexes. Compound 1 undergoes insertion reactions with diisopropylcarbodiimide and 2,6-dimethylphenylisocyanide to give (bisamidinate)imido complex 5 and (bisimino-acyl)imido complex 6, respectively. Treatment of compound 1 with B(C(6)F(5))(3) gives the zwitterionic tantalum complex [Bn(2)Ta=NCMe(3)][BnB(C(6)F(5))(3)] (7) which is stabilized by eta(6)-coordination of the benzyl triaryl borate anion. Coordination of the aryl anion can be displaced by three equivalents of pyridine to give the Lewis base complex 8. Treatment of compound 1 with [Ph(3)C][B(C(6)F(5))(4)] gives the cationic tantalum imido complex [Bn(2)Ta=NCMe(3)][B(C(6)F(5))(4)] (3). This salt forms insoluble aggregates unless trapped by THF coordination or an insertion reaction with an alkyne or an alkene. Cation 3 undergoes migratory insertion reactions with diphenylacetylene, phenylacetylene, norbornene, and cis-cyclooctene to give the corresponding alkenyl or modified alkyl imido complexes. The characterization of these products and the significance of these insertion reactions with respect to Ziegler-Natta polymerizations and hydroamination reactions are described.

Chromium(III) octaethylporphyrinato tetracarbonylcobaltate: a highly active, selective, and versatile catalyst for epoxide carbonylation.

The development of a highly active and selective porphyrin-based epoxide carbonylation catalyst, [(OEP)Cr(THF)2][Co(CO)4] (1; OEP = octaethylporphyrinato; THF = tetrahydrofuran), is detailed. Complex 1 is a separated ion pair composed of a tetracarbonylcobaltate anion and an octahedral chromium porphyrin complex axially ligated by two THF ligands. Regarding the carbonylation of epoxides to beta-lactones, catalyst 1 exhibits excellent turnover numbers (up to 10,000) and turnover frequencies (up to 1670 h(-1)), with regioselective carbonyl insertion occurring between the oxygen and the sterically less hindered carbon of the epoxide substrate. Complex 1 is highly tolerant of nonprotic functional groups, carbonylating an array of aliphatic and cycloaliphatic epoxides, as well as epoxides with pendant ethers, esters, and amides. With careful control of reaction conditions in the carbonylation of glycidyl esters, the exclusive production of either the beta- or gamma-lactone isomer was achieved. Through analysis of reaction stereochemistry, a mechanism for the formation of gamma-lactone products was proposed. Overall, a broad array of synthetically useful lactones has been synthesized in a rapid and selective fashion by catalytic carbonylation using [(OEP)Cr(THF)2][Co(CO)4].

Synthesis and characterization of mono beta-diketiminatosamarium amides and hydrocarbyls.

Reaction of SmCl3 with 1 eq of KL (L =[DippNC(Me)CHC(Me)NDipp]; Dipp = 2,6-i-Pr2C6H3) in THF afforded the dimeric samarium dichloride LSmCl2(THF)Cl2SmL (1) in high yield. Reactions of 1 with NaN(SiMe3)2, KNHAr (Ar = 2,4,6-t-Bu3C6H2), KBHEt3, and KCp*(Cp*= C5Me5) yielded various new complexes: LSmClN(SiMe3)2 (2), LSm[N(SiMe3)2]2 (3), LSmNHAr(HBEt3) (4), LSm(NHAr)2 (5), and LSmCp*Cl (6). Reaction of 1 with one eq of NaN(SiMe3)2 followed by treatment with excess AlMe3 afforded a unique bimetallic samarium tetramer Cl3L2Sm2(AlMe4)2Sm2L2Cl3 (7). Reaction of 6 with LiMe or LiCH2SiMe3 afforded LSmCp*Me (8) and LSmCp*CH2SiMe3 (9) in excellent yield. Methyl abstraction from with B(C6F5)3 in toluene yielded the cationic borate species (LSmCp*)[MeB(C6F5)3] (10). Molecular structures of 1-7 and 9 were determined by X-ray single crystal analysis.

A readily synthesized and highly active epoxide carbonylation catalyst based on a chromium porphyrin framework: expanding the range of available beta-lactones.

[reaction: see text] Catalytic carbonylation of epoxides to beta-lactones was effected by a highly active and selective bimetallic catalyst comprised of a chromium(III) porphyrin cation and a cobalt tetracarbonyl anion. The complex is readily synthesized from commercially available compounds in high yield. Carbonylation of numerous linear epoxides, as well as bicyclic epoxides derived from 8- and 12-membered hydrocarbons, proceeded with high activity, selectivity, and yield.

Anionic triazacyclononanes: new supporting ligands in main group and transition metal organometallic chemistry.

In the course of developing new ligands to support chemistry with main-group, transition and lanthanide elements, a number of research groups have focused attention on functionalized triazacyclononanes; this article provides a summary of the more recent findings with an emphasis on the organometallic chemistry of one particular class of tacn ligands, namely those involving the anionic tacn moiety.