Manganese and iron PCP pincer complexes – the influence of sterics on structure and reactivity

Eder, W. Ernst; Himmelbauer, Daniel; Stöger, Berthold; Veiros, Luı́s F.; Pignitter, Marc; Kirchner, Karl

doi:10.1039/d1dt02407h

Cited by 6 publications

(12 citation statements)

References 72 publications

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“…The synthesis of ligand precursors POCOP-Br (2-Br-1,3-( t Bu 2 PO) 2 -C 6 H 3 ) and PCP-Br (2-Br-1,3-( t Bu 2 PCH 2 ) 2 -C 6 H 3 ) has been reported previously; 8,9 the present reaction procedures were modified to produce target products in almost quantitative yields (Scheme 1). POCOP-Br was prepared from a reaction of 2-bromorecinol with t Bu 2 PCl in the presence of NEt 3 in 2-methyltetrahydrofuran (2-Me-THF) at 90 °C.…”

Section: Synthesis Of Ligand Precursorsmentioning

confidence: 96%

“…The preparation of PCP-Br was modified according to the synthetic method of PCP-H (1,3-( t Bu 2 PCH 2 ) 2 -C 6 H 4 ). [9][10][11] The reaction of 2-bromo-1,3-bis(bromomethyl)benzene with t Bu 2 PH in metha-nol at 60 °C afforded a phosphonium adduct which was subsequently deprotonated with Et 3 N to give Br-PCP in 97% yield.…”

Section: Synthesis Of Ligand Precursorsmentioning

confidence: 99%

“…The synthesis method was adapted from a literature procedure. 9 To a methanol (100 mL) solution of 2-bromo-1,3-bis(bromomethyl)benzene (4.000 g, 11.67 mmol) in a 350 mL J. Young Schlenk tube, t Bu 2 PH (3.838 g, 26.25 mmol) was added and the mixture was stirred at 60 °C for 12 h. After cooling to room temperature, NEt 3 (2.952 g, 29.17 mmol) was added to the resulting solution, and the mixture was stirred for 30 min.…”

Section: Paper Dalton Transactionsmentioning

confidence: 99%

“…4 However, as far as early-transition metals are concerned, PCP-type pincer complexes have remained much underexplored to date. [5][6][7][8][9] Schrock's group introduced the PCPtype ligand (POCOP: 2,6-( t Bu 2 PO) 2 -C 6 H 3 ) to a Mo complex and discovered the formation of a Mo nitride complex through reductive cleavage of dinitrogen. 5 Recently, Kirchner's group further extended the PCP-type pincer ligands to Cr, W and Mn complexes, some of which were found to be highly active for the catalytic hydrosilylation of ketones.…”

Section: Introductionmentioning

confidence: 99%

“…Hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and bond angles (°): Ti1-C1, 2.223(2); Ti1-P1, 2.6707(7); Ti1-P2, 2.6281(6); Ti1-C23, 2.196(3); Ti1-C27, 2.122(2); O1-C6, 1.403(3); O2-C2, 1.399(3); P1-Ti1-P2, 136.99(2); C23-Ti1-C1, 136.75(9); C27-Ti1-C1, 116.17(9).…”

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confidence: 99%

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Scandium, titanium and vanadium complexes supported by PCP-type pincer ligands: synthesis, structure, and styrene polymerization activity

et al. 2022

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Section: Synthesis Of Ligand Precursorsmentioning

confidence: 96%

Section: Synthesis Of Ligand Precursorsmentioning

confidence: 99%

Section: Paper Dalton Transactionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Scandium, titanium and vanadium complexes supported by PCP-type pincer ligands: synthesis, structure, and styrene polymerization activity

et al. 2022

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Solvothermal synthesis of cobalt PCP pincer complexes from [Co2(CO)8]

Schratzberger,

Himmelbauer,

Eder

et al. 2023

Monatsh Chem

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Treatment of [Co2(CO)8] with the ipso-substituted P(C-X)PY ligands (X = Br, Cl; R = iPr, tBu) bearing Y = NH and CH2 linkers under solvothermal conditions affords the five-coordinate Co(I) and Co(III) complexes [CoI(PCPY-R)(CO)2] and [CoIII(PCPY-R)X2]. The later are paramagnetic exhibiting a solution magnetic moment in the range of 3.0–3.3 μB which is consistent with a d6 intermediate spin system corresponding to two unpaired electrons. In the case of P(C-X)PY ligands (X = Br, Cl; R = tBu; Y = NH) the formation of the square planar Co(II) complex [Co(PCPNH-tBu)X] was favored. This complex gives rise to a magnetic moment of 1.8 μB being consistent with a d7 low spin system corresponding to one unpaired electron. All complexes are characterized by means of spectroscopic techniques (NMR, IR), HR-MS. Representative complexes were also characterized by X-ray crystallography. Graphical abstract

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Insertion of Molecular Oxygen into a Gold(III)–Hydride Bond

Phearman,

Ardon,

Goldberg

2024

J. Am. Chem. Soc.

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The use of molecular oxygen as an oxidant in chemical synthesis has significant environmental and economic benefits, and it is widely used as such in largescale industrial processes. However, its adoption in highly selective homogeneous catalytic transformations, particularly to produce oxygenated organics, has been hindered by our limited understanding of the mechanisms by which O 2 reacts with transition metals. Of particular relevance are the mechanisms of the reactions of oxygen with late transition metal hydrides as these metal centers are better poised to release oxygenated products. Homogeneous catalysis with gold complexes has markedly increased, and herein we report the synthesis and full characterization of a rare Au III −H, supported by a diphosphine pincer ligand ( tBu PCP = 2,6-bis(di-tert-butylphosphinomethyl)benzene). [( tBu PCP)Au III −H] + was found to cleanly react with molecular oxygen to yield a stable Au III −OOH complex that was also fully characterized. Extensive kinetic studies on the reaction via variable temperature NMR spectroscopy have been completed, and the results are consistent with an autoaccelerating radical chain mechanism. The observed kinetic behavior exhibits similarities to that of previously reported Pd II −H and Pt IV −H reactions with O 2 but is not fully consistent with any known O 2 insertion mechanism. As such, this study contributes to the nascent fundamental understanding of the mechanisms of aerobic oxidation of late metal hydrides.

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Manganese and iron PCP pincer complexes – the influence of sterics on structure and reactivity

Abstract: The syntheses of various manganese and iron PCP pincer complexes via a solvothermal oxidative addition methodology is described. Upon reacting [Mn2(CO)10] with the ligands (P(C-Br)PCH2-iPr) (1a) and (P(C-Br)PO-iPr) (1b), Mn(I)...

Cited by 6 publications

References 72 publications

Scandium, titanium and vanadium complexes supported by PCP-type pincer ligands: synthesis, structure, and styrene polymerization activity

Scandium, titanium and vanadium complexes supported by PCP-type pincer ligands: synthesis, structure, and styrene polymerization activity

Solvothermal synthesis of cobalt PCP pincer complexes from [Co2(CO)8]

Insertion of Molecular Oxygen into a Gold(III)–Hydride Bond

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