Reactivity of a T-Shaped Cobalt(I) Pincer-Complex

2021 ◽  
Author(s):  
Clemens Blasius ◽  
Regina Matveeva ◽  
Hubert Wadepohl ◽  
Lutz H Gade
Keyword(s):  
Carbon Monoxide ◽  
Neutral Ligand ◽  
Pincer Ligand ◽  
Pincer Complex

The reactivity of a paramagnetic T-shaped cobalt(I) complex, [(iPrboxmi)Co], stabilised by a monoanionic bis(oxazolinylmethylidene)-isoindolate (boxmi) NNN pincer ligand is described. The exposure to carbon monoxide as additional neutral ligand resulted...

scholarly journals Experimental and computational study of alkane dehydrogenation catalyzed by a carbazolide-based rhodium PNP pincer complex

2016 ◽  
Vol 7 (4) ◽  
pp. 2579-2586 ◽  
Author(s):  
David Bézier ◽  
Changjian Guan ◽  
Karsten Krogh-Jespersen ◽  
Alan S. Goldman ◽  
Maurice Brookhart
Keyword(s):  
Computational Study ◽  
Rhodium Complex ◽  
Pincer Ligand ◽  
Alkane Dehydrogenation ◽  
Pincer Complex

A rhodium complex based on the bis-phosphine carbazolide pincer ligand was investigated in the context of alkane dehydrogenation and in comparison with its iridium analogue.

Synthesis, characterization, photophysical properties, and catalytic activity of an SCS bis(N-heterocyclic thione) (SCS-NHT) Pd pincer complex

2015 ◽  
Vol 44 (32) ◽  
pp. 14475-14482 ◽  
Author(s):  
Ginger E. Tyson ◽  
Kenan Tokmic ◽  
Casey S. Oian ◽  
Daniel Rabinovich ◽  
Henry U. Valle ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Photophysical Properties ◽  
Pincer Ligand ◽  
Pincer Complex

The first SCS-NHT pincer ligand and its Pd complex.

Divergent Reactivity of CO2 and CO and Related Substrates at the Nickel Carbon Double Bond of (PCcarbeneP)Ni(II) Pincer Complexes

2018 ◽  
Author(s):  
Etienne A. LaPierre ◽  
Warren Piers ◽  
Chris Gendy
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Double Bond ◽  
Transfer Reactions ◽  
Pincer Complexes ◽  
Pincer Ligand ◽  
Group Transfer ◽  
Ligand Structure ◽  
Carbon Double Bond

The addition of carbon monoxide (CO), carbon dioxide (CO<sub>2</sub>) and isoelectronic isocyanide and isocyanates to the nickel carbene bond in PC<sub>carbene</sub>P pincer complexes is reported. For CO and CNR, irreversible group transfer reactions are observed, while for CO<sub>2</sub>, a reversible 2+2 addition to the carbene moiety occurs. The course of the CO and CO<sub>2</sub> reactions are strongly affected by the nature of the PC<sub>carbene</sub>P pincer ligand framework and a new more rigid ligand based on a 10,10-dimethyl-9,10-dihydroanthracene core was designed in order to study these reactions, illustrating the profound effect of small changes in ligand structure on reaction outcomes.

Crystalline Cu(ii) metal–organic frameworks based on a carboxamide pincer ligand and an NCONCON–Pd(ii) pincer complex

CrystEngComm ◽  
2021 ◽  
Author(s):  
Siphelele S. P. Malaza ◽  
Gift Mehlana ◽  
Ocean Cheung ◽  
Roger Hunter ◽  
Banothile C. E. Makhubela
Keyword(s):  
Carbon Dioxide ◽  
Metal Organic Frameworks ◽  
Organometallic Complexes ◽  
Carbon Dioxide Conversion ◽  
Pincer Ligand ◽  
Pincer Complex ◽  
Metal Organic

Two copper MOFs based on carboxamide linkers are presented. This work shows how organometallic complexes with carboxylate functionalities can be repurposed to produce crystalline MOFs which can be used in carbon dioxide conversion.

scholarly journals Metal–ligand cooperative activation of nitriles by a ruthenium complex with a de-aromatized PNN pincer ligand

2016 ◽  
Vol 45 (40) ◽  
pp. 16033-16039 ◽  
Author(s):  
Linda E. Eijsink ◽  
Sébastien C. P. Perdriau ◽  
Johannes G. de Vries ◽  
Edwin Otten
Keyword(s):  
Ruthenium Complex ◽  
Pincer Ligand ◽  
Pincer Complex ◽  
Cooperative Activation ◽  
Metal Ligand

Metal–ligand cooperative activation of nitriles by a de-aromatized Ru pincer complex leads to equilibrium mixtures (tautomers) as a result of ligand deprotonation by the Brønsted basic Ru-ketimido moiety.

Improved synthesis of pincer ligand precursor, and synthesis and structural characterization of terphenyl scaffolded S–C–S palladium pincer complex

2009 ◽  
Vol 12 (12) ◽  
pp. 1171-1174 ◽  
Author(s):  
Paul M. Schroder ◽  
Thomas F. Spilker ◽  
Wilson Luu ◽  
James B. Updegraff ◽  
Man Lung Kwan ◽  
...  
Keyword(s):  
Structural Characterization ◽  
Pincer Ligand ◽  
Pincer Complex

scholarly journals {Bis[2-(diisopropylphosphanyl)ethyl]amine}carbonyl(tetrahydroborato)cobalt(I)

IUCrData ◽  
2018 ◽  
Vol 3 (3) ◽  
Author(s):  
Kathrin Junge ◽  
Andrea Cingolani ◽  
Anke Spannenberg ◽  
Matthias Beller
Keyword(s):  
Carbon Monoxide ◽  
Van Der Waals ◽  
Van Der Waals Forces ◽  
Tridentate Ligand ◽  
Coordination Geometry ◽  
Pincer Complex ◽  
Ethyl Amine

In the structure of title borohydride pincer complex, [Co(BH4)(C16H37NP2)(CO)], the cobalt(I) metal exhibits a distorted square-pyramidal coordination geometry with the basal positions occupied by the P and N atoms of the tridentate ligand and by the C atom of the carbon monoxide ligand. In the crystal, molecules interact only by van der Waals forces.

Divergent Reactivity of CO2 and CO and Related Substrates at the Nickel Carbon Double Bond of (PCcarbeneP)Ni(II) Pincer Complexes

2018 ◽  
Author(s):  
Etienne A. LaPierre ◽  
Warren Piers ◽  
Chris Gendy
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Double Bond ◽  
Transfer Reactions ◽  
Pincer Complexes ◽  
Pincer Ligand ◽  
Group Transfer ◽  
Ligand Structure ◽  
Carbon Double Bond

The addition of carbon monoxide (CO), carbon dioxide (CO<sub>2</sub>) and isoelectronic isocyanide and isocyanates to the nickel carbene bond in PC<sub>carbene</sub>P pincer complexes is reported. For CO and CNR, irreversible group transfer reactions are observed, while for CO<sub>2</sub>, a reversible 2+2 addition to the carbene moiety occurs. The course of the CO and CO<sub>2</sub> reactions are strongly affected by the nature of the PC<sub>carbene</sub>P pincer ligand framework and a new more rigid ligand based on a 10,10-dimethyl-9,10-dihydroanthracene core was designed in order to study these reactions, illustrating the profound effect of small changes in ligand structure on reaction outcomes.

scholarly journals Late Transition Metal Complexes of Pyridyldiphosphines

2021 ◽  
Author(s):  
◽  
Teresa Florence Vaughan
Keyword(s):  
Carbon Monoxide ◽  
Strong Acid ◽  
Hard Metal ◽  
Water Soluble ◽  
Pincer Complexes ◽  
Pyridyl Nitrogen ◽  
Pincer Complex ◽  
Chloride Ligand ◽  
Coordination Behaviour ◽  
Pcp Pincer

<p>This thesis provides an account of research into the properties of pyridyldiphosphines with o-xylene and m-xylene backbones. The coordination behaviour of the o-xylene based ligand with platinum, palladium, silver, rhodium and iridium metal centres has been studied, with an emphasis on whether the presence of the pyridyl rings affects the products formed. Platinum and palladium pincer complexes have been synthesised and the intermediates investigated. The formation of trimetallic complexes with these ligands acting as bridging ligands has also been explored.  Two new pyridyldiphosphines, o-C₆H₄(CH₂PPy₂)₂ (3) and m-C₆H₄(CH₂PPy₂)₂ (4), and one known pyridyldiphosphine, PPy₂(CH₂)₃PPy₂ (5), have been synthesised via an improved method. Tris(2-pyridyl)phopshine was reacted with a lithium dispersion to give LiPPy₂, which was then reacted with the appropriate dichloride or dibromide compound to yield the desired ligand. The phosphine selenides of 3 and 4 were synthesised and the ¹J PSe values of 738 and 742 Hz indicated these ligands were less basic than PPh₃. While the ligands themselves were not water-soluble, protonation by a strong acid, such as HCl or H₂C(SO₂CF₃)₃, rendered them soluble in water.  A series of [MX₂(PP)] complexes (where M = Pt, X = Cl, I, Me, Et, PP = 3, 5; M = Pd, X = Cl, Me PP = 3, 5) were synthesised. Complexes of 3 displayed dynamic behaviour in solution which was attributed to the backbone of the ligand inverting. When [PtMeCl(PP)] (27) was reacted with NaCH(SO₂CF₃)₂ no evidence for the coordination of the pyridyl nitrogens was observed. The synthesis of a series of unsymetrical [PtMeL(PP)]⁺ complexes enabled the comparison of the cis and trans influences of a range of ligands. The following cis influence series was compiled based on ³¹P NMR data of these complexes: Py ≈ Cl > SEt₂ > PTA > PPh₃. Reaction of 27 with NaCH(SO₂CF₃)₂ and carbon monoxide slowly formed an acyl complex, where the CO had inserted in the Pt–Me bond.  The bis-chelated complexes [M(PP)₂] where M = Pt, Pd, and [Ag(PP)₂]⁺ were formed. In these complexes 3 acted as a diphosphine ligand and there was no evidence for any interaction between the pyridyl nitrogen atoms and the metal centre.  Reaction of 3 with [Ir(COD)(μ-Cl)]₂ formed [IrCl(PP)(COD)] (42). When the chloride ligand in 42 was abstracted, the pyridyl nitrogens were able to interact with the iridium centre faciliating the isomerisation of the 1,2,5,6-ƞ⁴-COD ligand to a 1-к-4,5,6-ƞ³-C₈H₁₂ ligand. The X-ray crystal structure of [Ir(1-к-4,5,6-ƞ³-C₈H₁₂)(PPN)]BPh₄ (43) confirmed the P,P,N chelation mode of the ligand. In solution, 43 displayed hemilabile behaviour, with the pyridyl nitrogens exchanging at a rate faster than the NMR time scale at room temperature. The coordinated pyridyl nitrogen was able to be displaced by carbon monoxide to form [Ir(1-к-4,5,6-ƞ³-C₈H₁₂)(CO)(PP)]⁺.  A series of [PtXY(μ-PP)]₂ complexes, where X = Y = Cl, Me, X = Cl, Y = Me and PP = 4, were formed initially when 4 was reacted with platinum(II) complexes. When heated, the dimers containing methyl ligands eliminated methane to form [PtX(PCP)] pincer complexes, X = Cl (49), Me (51). When the chloride ligand in 49 was abstracted no evidence of pyridyl nitrogen coordination was observed. Protonation of 49 did not yield a water-soluble pincer complex. The [PdCl₂(μ-PP)]₂ complex readily metallated when heated to give the pincer complex [PdCl(PCP)].  Given pyridyl nitrogen atoms are known to be good ligands for “hard” metal centres, the ability of the pyridyl nitrogens in 3 and 4 to coordinate to metal centres was investigated. While complexes with chloride ligands were found to form insoluble products, the synthesis of [(PtMe₂)₃(PP)], from the reaction of either 3 or [PtMe₂(PP)] (17) with dimethyl(hexa-1,5-diene)platinum, proceeded smoothly through a dimetallic intermediate. The same reactivity was observed in the synthesis of [(PtMe₂)₂PtMe(PCP)]. In contrast, the cationic heterotrimetallic complexes [{M(COD)}₂PtMe(PP)]²⁺ and [{M(COD)}₂PtMe(PCP)]²⁺, where M = Rh or Ir, were synthesised without the detection of any intermediates. However, dimetallic complexes were formed as part of a mixture when 17 or 51 was reacted with one equivalent of the appropriate metal complex.</p>

Acridine based (S,N,S) pincer ligand: designing silver(i) complexes for the efficient activation of A3 (aldehyde, alkyne and amine) coupling

2015 ◽  
Vol 44 (4) ◽  
pp. 1962-1968 ◽  
Author(s):  
Om Prakash ◽  
Hemant Joshi ◽  
Umesh Kumar ◽  
Alpesh K. Sharma ◽  
Ajai K. Singh
Keyword(s):  
Catalytic Efficiency ◽  
Pincer Ligand ◽  
Pincer Complex ◽  
Amine Coupling

The catalytic efficiency for the A3 reaction with complexes 1 and 2, which have been newly synthesized and structurally characterized, is highest for the pincer complex 2.

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