Bis(imino)phosphanes: Synthesis and Coordination Chemistry

Dijk, Tom van; Rong, Mark K.; Borger, Jaap E.; Nieger, Martin; Slootweg, J. Chris; Lammertsma, Koop

doi:10.1021/acs.organomet.6b00063

Cited by 12 publications

(6 citation statements)

References 68 publications

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“…The Th IV metal center retained one of its phosphido ligands; however, the t BuCN inserted into the other Th−P bond, which was accompanied by the migration of the proton from phosphorus to the nitrogen atom of the nitrile, and the formation of a P−C bond. The newly formed phosphaamidinate coordinates to the metal center via a delocalized [ κ 2 ‐( N , P )‐N(H)C( t Bu)P(Mes)] 1− ligand. During the crystallographic refinement, a proton in close proximity to the coordinated nitrogen atom was located, whereas no such electron density was observed near the phosphorus of the new ligand.…”

Section: Figuresupporting

confidence: 62%

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

et al. 2018

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We report intramolecular proton transfer reactions to functionalize carbon monoxide and tert‐butyl nitrile from a bis(phosphido) thorium complex. The reaction of (C5Me5)2Th[PH(Mes)]2, Mes=2,4,6‐Me3C6H2, with 1 atm of CO yields (C5Me5)2Th(κ2‐(O,O)‐OCH2PMes‐C(O)PMes), in which one CO molecule is inserted into each thorium–phosphorus bond. Concomitant transfer of two protons, formerly coordinated to phosphorus, are now bound to one of the carbon atoms from one of the inserted CO molecules. DFT calculations were employed to determine the lowest energy pathway. With tert‐butyl nitrile, tBuCN, only one nitrile inserts into a thorium–phosphorus bond, but the proton is transferred to nitrogen with one phosphido remaining unperturbed affording (C5Me5)2Th[PH(Mes)][κ2‐(P,N)‐N(H)C(CMe3)P(Mes)]. Surprisingly, reaction of this compound with KN(SiMe3)2 removes the proton bound to nitrogen, not phosphorus.

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Section: Figuresupporting

confidence: 62%

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

et al. 2018

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“…Celite and 4 Å molecular sieves were activated under vacuum overnight at 200 °C. ZrCl 4 (THF) 2 , KC 8 , N 1 ‐(2‐aminoethyl)‐ N 1 , N 2 , N 2 ‐trimethylethane‐1,2‐diamine ( 1 ), and 1‐chloro‐2‐(2,6‐diisopropylphenylimino)‐2,2‐dimethylpropane were prepared according to the reported procedures. NaN 3 was dried by stirring in anhydrous THF overnight, washed with anhydrous Et 2 O and pentane and then evacuated at room temperature overnight.…”

Section: Methodsmentioning

confidence: 99%

Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand

Kurogi

Chu

Chen

et al. 2019

Chemistry An Asian Journal

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As terically encumbering multidentate b-diketiminato ligand, tBu L2 ( tBu L2=[ArNC(tBu)CHC(tBu)NCH 2 CH 2 N(Me)-CH 2 CH 2 NMe 2 ] À ,A r = 2,6-iPr 2 C 6 H 3 ), is reported in this study along with its coordination chemistry to zirconium(IV). Using the lithio salt of this ligand,L i( tBu L2) (4), the zirconium(IV) precursor ( tBu L2)ZrCl 3 (6)c ould be readily prepared in 85 % yield ands tructurally characterized.R eduction of 6 with 2equiv of KC 8 resulted in formationo ft he terminal and mononuclear zirconium imide-chloride [C(tBu)CHC(t-Bu)NCH 2 CH 2 N(Me)CH 2 CH 2 NMe 2 ]Zr(=NAr)(Cl) (7)a st he result of reductive C=Nc leavage of the imino fragment in the multidentate ligand tBu L2 by an elusiveZ r II species( tBu L2)ZrCl (A). The azabutadienyl ligand in 7 can be further reduced by 2e À with KC 8 to afford the anionic imide [K(THF) 2 ]{[CH(tBu)CHC(tBu)NCH 2 CH 2 N(Me)CH 2 CH 2 N(Me)CH 2 ]-Zr=NAr} (8-2THF)i n4 2% isolated yield. Complex 8-2THF results from the oxidative addition of an amine CÀHb ond followed by migration to the vinylic group of the formal [C(tBu)CHC(tBu)NCH 2 CH 2 N(Me)CH 2 CH 2 NMe 2 ] À ligand in 7.A ll halidesi n6 can be replaced with azides to afford ( tBu L2)Zr(N 3 ) 3 (9)w hichw as structurally characterized, and reductionw ith two equiv of KC 8 also results in C=Nb ond cleavage of tBu L2 to form [C(tBu)CHC(tBu)NCH 2 CH 2 N-(Me)CH 2 CH 2 NMe 2 ]Zr(=NAr)(N 3 )( 10), instead of the expected azide disproportionation to N 3À and N 2 .S olid-state single crystal structural studies confirm the formation of mononuclear and terminal zirconium imido groups in 7, 8-Et 2 O,a nd 10 with Zr=NAr distances being 1.8776(10), 1.9505(15), and 1.881(3) ,r espectively.Scheme1.Multidentate ligands havingthe b-diketiminato motif,where Ar represents iPr 2 C 6 H 3 .[a] Dr.Scheme2.Synthetic entry to the lithio salt 4 of the b-diketiminato ligand tBu L2 starting from the trisamino precursor 1,which can be prepared by two separate reactionss temming from N,N,N'-trimethylethylenediamine.

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“…Solvents are removed under reduced pressure using a rotavapor, and the resulted residue was purified by column chromatography. The following amides were prepared and characterized by NMR analyses and data compared with the reported literature: N-(2,3-dimethylphenyl)acetamide, 34 N-mesitylacetamide, 35 N-(2,6-diisopropylphenyl) acetamide, 36 N-(4-methoxyphenyl) acetamide, 37 N-(2-(phenylthio)phenyl) acetamide, 38 N-(2-fluorophenyl) acetamide, 39 N-(4-chlorophenyl)acetamide, 40 N-(4-bromophenyl)acetamide, N-phenylpropanamide, 41 and N,2-diphenylacetamide. 42 General Procedure for Optimization of α-Alkenylation of Amides Using Alcohols.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Manganese(I) Catalyzed α-Alkenylation of Amides Using Alcohols with Liberation of Hydrogen and Water

Pandia

Gunanathan

2021

J. Org. Chem.

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Herein, unprecedented manganese-catalyzed direct α-alkenylation of amides using alcohols is reported. Aryl amides are reacted with diverse primary alcohols, which provided the α,β-unsaturated amides in moderate to good yields with excellent selectivity. Mechanistic studies indicate that Mn(I) catalyst oxidizes the alcohols to their corresponding aldehydes and also plays an important role in efficient CC bond formation through aldol condensation. This selective olefination is facilitated by metal–ligand cooperation by the aromatization–dearomatization process operating in the catalytic system. Biorenewable alcohols are used as alkenylation reagents for the challenging α-alkenylation of amides with the highly abundant base metal manganese as a catalyst, which results in water and dihydrogen as the only byproduct, making this catalytic transformation attractive, sustainable, and environmentally benign.

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Bis(imino)phosphanes: Synthesis and Coordination Chemistry

Cited by 12 publications

References 68 publications

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

Functionalization of Carbon Monoxide and tert‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

Neutral and Anionic Monomeric Zirconium Imides Prepared via Selective C=N Bond Cleavage of a Multidentate and Sterically Demanding β‐Diketiminato Ligand

Manganese(I) Catalyzed α-Alkenylation of Amides Using Alcohols with Liberation of Hydrogen and Water

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