Lan-Chang Liang

Amido phosphine complexes of zinc: synthesis, structure, and catalytic ring-opening polymerization of ε-caprolactone

A series of diarylamido phosphine ligands of the type N-(2-dihydrocarbylphosphinophenyl)-2,6-dialkylanilide 1a-d have been prepared and employed to investigate the coordination chemistry of zinc. Protonolysis of ZnMe2 with one equivalent of N-(2-diphenylphosphinophenyl)-2,6-dimethylaniline (H[1a]) produced a mixture of [1a]ZnMe (2a) and Zn[1a]2 (4a), whereas that involving ZnEt2 gave exclusively the three-coordinate [1a]ZnEt (3a). In contrast, treatment of ZnR2 (R = Me, Et) with N-(2-diphenylphosphinophenyl)-2,6-diisopropylaniline (H[1b]), N-(2-diisopropylphosphinophenyl)-2,6-dimethylaniline (H[1c]), or N-(2-diisopropylphosphinophenyl)-2,6-diisopropylaniline (H[1d]) under similar conditions generated quantitatively the corresponding three-coordinate zinc methyl 2b-d and zinc ethyl 3b-d. The bis-ligand complexes 4a,b,d were isolated by either protonolysis of alkyls 2-3 with one equivalent of H[1] or metathesis of ZnX2 (X = Cl, OAc) with the corresponding lithium derivatives 5. Attempts to prepare [1a-d]ZnX (X = Cl, OAc) were not successful regardless of stoichiometry of the starting materials employed. Alcoholysis of zinc alkyls 2-3 led undesirably to protonation on the amido nitrogen donor of 1, highlighting perhaps its higher basicity than alkyls. The reaction of ZnCl2 with H[1c] generated the phosphorus-bound adduct {H[1c]ZnCl(mu-Cl)}2 (6c). Interestingly, attempts to deprotonate 6c with n-BuLi produced unexpectedly the alkylated product [1c]Zn(n-Bu) (7c) instead of [1c]ZnCl; analogous reactions employing NEt3 led to Lewis base substitution to give H[1c] and [ZnCl2(NEt3)]2. Structural characterization of all new compounds was achieved by multi-nuclear NMR spectroscopy (1H, 13C, 31P, and 7Li) and X-ray crystallography (2c-d, 3c, 4d, 5c-d, and 6c) where appropriate. On the basis of the NMR and X-ray data, in combination with the synthetic investigations, the steric nature of these amido phosphine ligands is recognized to follow the order of 1a < 1b < 1c < 1d. Interestingly, zinc alkyls 2-3 are all active initiators for catalytic ring-opening polymerization of ε-caprolactone whereas the bis-ligand complexes 4 are not.

Titanium complexes of tridentate aminebiphenolate ligands containing distinct N-alkyls: profound N-substituent effect on ring-opening polymerization catalysis.

The synthesis, structural characterization, and reactivity studies of titanium complexes supported by tridentate amine biphenolate ligands of the type [RN(CH(2)-2-O-3,5-C(6)H(2)(tBu)(2))(2)](2-) {[R-ONO](2-); R = tBu (1a), iPr (1b), nPr (1c)} are described. Alcoholysis of Ti(OiPr)(4) with H(2)[1a-1c] in diethyl ether solutions at 25 °C generates quantitatively the corresponding [R-ONO]Ti(OiPr)(2) (2a-2c) as a yellow crystalline solid. X-ray diffraction studies of 2b and 2c showed them to be five-coordinate, trigonal-bipyramidal species. Ring-opening polymerization of ε-caprolactone (ε-CL) catalyzed by 2b and 2c proved to be living, as evidenced by the narrow molecular weight distributions of the derived polymers and the linear dependence of number-averaged molecular weights on the monomer-to-catalyst ratios or polymerization time. Kinetic studies revealed that the polymerization rates are first-order in the concentration of ε-CL and first-order in that of 2b and 2c. The propagation rate of 2c is ca. 15 times faster than that of 2b, highlighting a profound substituent effect of primary versus secondary N-alkyls. In sharp contrast, reactions employing catalytic 2a produce either low-molecular-weight oligomers or polymers characteristic of somewhat wider molecular weight distributions, depending on the polymerization temperatures.

Zirconium and hafnium complexes containing N-alkyl substituted amine biphenolate ligands: coordination chemistry and living ring-opening polymerization catalysis

The coordination chemistry of zirconium and hafnium complexes containing the tridentate amine biphenolate ligands [RN(CH2-2-O-3,5-C6H2(tBu)2)2](2-) ([R-ONO](2-); R = tBu (1a), iPr (1b), nPr (1c)) featuring distinct N-alkyl substituents is described. Alcoholysis of Zr(OiPr)4(HOiPr) or Hf(OiPr)4(HOiPr) with H2[1a] in diethyl ether solutions at -35 °C generates the corresponding five-coordinate [1a]M(OiPr)2 (M = Zr (2a), Hf (3a)) in high isolated yield. Similar reactions employing H2[1b] produce six-coordinate [1b]M(OiPr)2(HOiPr) (M = Zr (2b·HOiPr), Hf (3b·HOiPr)) as an isopropanol adduct. Repetitive trituration of 2b·HOiPr and 3b·HOiPr with diethyl ether gives five-coordinate 2b and 3b, respectively. Treatment of M(OiPr)4(HOiPr) with H2[1c] under similar conditions affords six-coordinate [1c]M(OiPr)2(HOiPr) (M = Zr (2c·HOiPr), Hf (3c·HOiPr)), subsequent recrystallization of which from acetonitrile-diethyl ether solutions leads to acetonitrile adducts 2c·MeCN and 3c·MeCN. Reactivity studies of these zirconium and hafnium complexes revealed that they are all active catalysts for ring-opening polymerization of ε-caprolactone. Among them, the N-isopropyl derived complexes are most reactive. Polymerizations catalyzed by 2b, 3b and 3c·MeCN were proved to be living. The X-ray structures of 2a·HOiPr, 2a·MeCN, 2c·HOiPr, 2c·MeCN, and 3c·MeCN are presented.

A terminal nickel(II) anilide complex featuring an unsymmetrically substituted amido pincer ligand: synthesis and reactivity

This work describes preparation and reaction chemistry of a terminal nickel(II) anilide complex supported by an unsymmetrically substituted diarylamido diphosphine ligand, [N(o-C(6)H(4)PPh(2))(o-C(6)H(4)P(i)Pr(2))](-) ([Ph-PNP-(i)Pr](-)). Treatment of NiCl(2)(DME) with H[Ph-PNP-(i)Pr] in THF at room temperature produced [Ph-PNP-(i)Pr]NiCl as green crystals in 82% yield. Salt metathesis of [Ph-PNP-(i)Pr]NiCl with LiNHPh(THF) in THF at -35 °C generated cleanly [Ph-PNP-(i)Pr]NiNHPh as a greenish blue solid. The anilide complex deprotonates protic (e.g., PhOH and PhSH) and aprotic (e.g., trimethylsilylacetylene, phenylacetylene, and acetonitrile) acids in benzene at room temperature to give quantitatively [Ph-PNP-(i)Pr]NiX (X = OPh, SPh, C≡CSiMe(3), C≡CPh, CH(2)CN). In addition, [Ph-PNP-(i)Pr]NiNHPh also behaves as a nucleophile to react with acetyl chloride to yield [Ph-PNP-(i)Pr]NiCl and N-phenylacetamide quantitatively. Carbonylation of [Ph-PNP-(i)Pr]NiNHPh with carbon monoxide affords cleanly the carbamoyl derivative [Ph-PNP-(i)Pr]Ni[C(O)NHPh]. The relative bond strengths of Ni-E in [Ph-PNP-(i)Pr]NiEPh (E = NH, O, S, C≡C) are assessed and discussed.

Catalytic Sonogashira couplings mediated by an amido pincer complex of palladium

This work describes the efficacy of [PNP]PdCl (1a), where [PNP]− = bis(2-diphenylphosphinophenyl)amide, as a catalyst precursor for Csp–Csp2 bond-forming cross-coupling reactions of terminal alkynes with aryl halides in the presence of copper bromide and aliphatic amines in ethereal solutions under mild conditions. This catalysis is compatible with acetylenes that are alkyl, alkenyl, (hetero)aryl, or silyl substituted and aryl iodides or bromides that are electronically activated, neutral, or deactivated. The low reaction constants of 0.82(6) and 0.97(7) obtained from Hammett plots of competitive reactions employing electronically distinct aryl iodides and terminal alkynes, respectively, are likely suggestive of irrelevance of the rate-determining step in these catalytic transformations to oxidative addition of aryl halides or generation of mono-substituted acetylides. In sharp contrast, reactions employing a phosphorus-bound isopropyl derived 1b gave rather unsatisfactory results, highlighting a profound phosphorus substituent effect on this aryl alkynylation catalysis.

Zirconium and hafnium complexes containing N-alkyl-substituted amine biphenolate ligands: unexpected ligand degradation and divergent complex constitutions governed by N-alkyls.

The reactivity and thermal stability of zirconium and hafnium complexes containing the N-alkyl-substituted amine biphenolate ligands of the type [RN(CH2-2-O-3,5-C6H2(tBu)2)2](2-) ([R-ONO](2-); R = tBu (1a), iPr (1b), or nPr (1c)) were investigated. The reactions of either [1a]M(OiPr)2 (M = Zr or Hf) with equimolar H2[1a] or M(OiPr)4(HOiPr) (M = Zr or Hf) with 2 equiv of H2[1a] at 25 °C in diethyl ether or 80 °C in toluene afford moderate yields of colorless crystals of M[1a](OiPr)(iPrOCH2-2-O-3,5-C6H2(tBu)2) (M = Zr (4a) or Hf (5a)). Controlled experiments revealed that the production of 4a and 5a proceeds via unexpected thermal degradation of H2[1a] that produces a highly reactive, transient ortho-quinone methide intermediate. Similar reactions employing H2[1b] and H2[1c], however, led to the formation of homoleptic bis-ligand complexes Zr[1b]2 (8b) and M[1c]2 (M = Zr (8c) or Hf (9c)) as colorless crystals. Decisive factors governing these divergent reaction pathways and complex constitutions are discussed. The X-ray structures of 4a, 5a, 8b, 8c, and 9c are presented.

Homo- and Heteropolynuclear Clusters of Phosphine Triphenolates

The synthesis and structural characterization of a series of homo- and heteropolynuclear clusters constructed with a potentially tetradentate phosphine triphenolate ligand are presented. Treatment of tris(3,5-di-tert-butyl-2-hydroxyphenyl)phosphine (H3[O3P]) with 3 equiv of nBuLi in diethyl ether at -35 °C affords hexanuclear Li6[O3P]2(OEt2)2 (1) as colorless crystals. In situ lithiation of H3[O3P] with 3 equiv of nBuLi in THF at -35 °C followed by metathetical reactions with MnCl2 or NiCl2(DME) gives crystals of forest green pentanuclear MnLi4[O3P]2(THF)3 (2) or dark brown tetranuclear Ni2Li2[O3P]2(THF)2 (3), respectively. Alkane elimination of ZnR2 (R = Me, Et) with H3[O3P] in THF at 25 °C generates high yields of colorless crystalline trinuclear Zn3[O3P]2(THF)2 (4). The cluster structures of 1-4 were all determined by single crystal X-ray diffraction studies. These molecules represent the first examples of metal complexes supported by phosphine triphenolate derivatives. The cluster 2 contains a paramagnetic core of high spin Mn(II) (S = 5/2) as indicated by solution and solid state magnetic susceptibility measurements.

Aluminum complexes containing biphenolate phosphine ligands: synthesis and living ring-opening polymerization catalysis

This report describes the synthesis, structure, and reactivity of aluminum complexes containing tridentate biphenolate phosphine ligands of the type [RP(2-O-3,5-C6H2tBu2)2]2- (R = tBu (2a), Ph (2b)). Alkane elimination of AlMe3 with one equiv. of H2[2a] or H2[2b] in THF at 0 °C cleanly affords colorless crystalline [2a]AlMe(THF) (3a) and [2b]AlMe(THF) (3b), respectively. An X-ray diffraction study of 3a showed it to be a five-coordinate THF-bound species, whose coordination geometry is best described as trigonal bipyramidal, having the phosphorus donor and THF at axial positions. Treatment of either in situ prepared or isolated methyl complexes 3a,b with one equiv. of benzyl alcohol in toluene or THF generated their corresponding benzyloxides {[2a,b]Al(μ2-OCH2Ph)}2 (4a,b). An X-ray diffraction study of 4a revealed a dimeric structure, in which the coordination geometry of aluminum is also distorted trigonal bipyramidal with the tridentate 2a ligand being facially bound. In the presence of one equiv. of benzyl alcohol, complex 3a is a competent catalyst precursor for the living ring-opening polymerization of ε-caprolactone (ε-CL) and rac-lactide (rac-LA), producing poly(ε-caprolactone) and poly(rac-lactide), respectively, in a controlled manner. As such, well-defined block copolymers of ε-CL with rac-LA can also be prepared by catalytic 3a. Kinetic studies revealed that 3a catalyzes the polymerization of rac-lactide at a rate 2-fold faster than that of 3b, indicating the significance of the P-substituent effect on this catalysis. Interestingly, the polymerization rate of rac-lactide by 3a is 16.5 times faster than that of l-lactide under otherwise identical conditions.

Organoaluminium complexes incorporating an amido phosphine chelate with a pendant amine arm

The palladium-catalyzed aryl amination of 1-bromo-2-fluorobenzene with N,N-dimethylethylenediamine quantitatively produces N-(dimethylaminoethyl)-2-fluoroaniline, which subsequently reacts with KPPh2 in 1,4-dioxane to afford N-(dimethylaminoethyl)-2-diphenylphosphinoaniline (H[PNN]). The reactions of trialkylaluminium with H[PNN] in toluene generate the corresponding aluminium dialkyl complexes [PNN]AlR2 (R = Me, Et, i-Bu). The solution NMR spectroscopic and X-ray crystallographic studies are indicative of a trigonal bipyramidal geometry for these aluminium complexes in which the amino nitrogen atom is trans to the phosphorus donor of the [PNN]- ligand. This study presents rare examples of structurally characterized, five-coordinate aluminium hydrocarbyl complexes supported by phosphine-derived ligands.