Organoruthenium Complexes Containing Phosphinodicarboxamide Ligands

被引：0

作者：

Nolla-Saltiel, Roberto ^{[1
,2
]}

Geer, Ana M. ^{[1
,3
]}

Sharpe, Helen R. ^{[1
]}

Huke, Cameron D. ^{[1
]}

Taylor, Laurence J. ^{[1
]}

Linford-Wood, Thomas G. ^{[1
]}

James, Ashleigh ^{[1
]}

Allen, Jamie ^{[1
]}

Lewis, William ^{[1
,4
,5
]}

Blake, Alexander J. ^{[1
]}

Mcmaster, Jonathan ^{[1
]}

Kays, Deborah L. ^{[1
]}

机构：

[1] Univ Nottingham, Sch Chem, Univ Pk, Nottingham NG7 2RD, England

[2] Queens Univ, Dept Chem, Kingston, ON K7L 3N6, Canada

[3] Univ Zaragoza, CSIC, Inst Sintesis Quim & Catalisis Homogenea ISQCH, Dept Quim Inorgan, Pedro Cerbuna 12, Zaragoza 50009, Spain

[4] Univ Sydney, Sch Chem, F11 Eastern Ave, Sydney, NSW 2006, Australia

[5] Univ Sydney, Sydney Analyt, F09 Eastern Ave, Sydney, NSW 2006, Australia

来源：

INORGANICS | 2023年 / 11卷 / 09期

基金：

英国工程与自然科学研究理事会;

关键词：

phosphinocarboxamide; metallacycle; ruthenium; P ligands; coordination chemistry; X-RAY-STRUCTURE; COORDINATION CHEMISTRY; TRANSFER HYDROGENATION; PHOSPHINECARBOXAMIDE; CUMULENYLIDENE; APPROXIMATION; ALLENYLIDENE; ENERGY;

D O I：

10.3390/inorganics11090372

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ruthenium complexes of phosphinocarboxamide ligands, and their use to form metallacycles using halide abstraction/deprotonation reactions are reported. Thus, [Ru(p-cym){PPh2C(=O)NHR}Cl2; R = iPr (1), Ph (2), p-tol (3)] and [Ru(p-cym){PPh2C(=O)N(R)C(=O)N(H)R}Cl2; R = Ph (4), p-tol (5)] were synthesized from [(p-cym)RuCl2]2 (p-cym = para-cymene) and phosphinocarboxamides or phosphinodicarboxamides, respectively. Single-crystal X-ray diffraction measurements on 1-5 reveal coordination to ruthenium through the phosphorus donor, with an intramolecular hydrogen bond between the amine-bound proton and a metal-bound chloride. Six-membered metallacycles formed by halide abstraction/deprotonation of complexes 4 and 5 afforded [Ru(p-cym){& kappa;2-P,N-PPh2C(=O)N(R)C(=O)NR}Cl] [R = Ph (6), p-tol (7)]. These species exist as a mixture of two rotational isomers in solution, as demonstrated by NMR spectroscopy.

引用

页数：12

共 46 条

[1] NNP-Type Pincer Imidazolylphosphine Ruthenium Complexes: Efficient Base-Free Hydrogenation of Aromatic and Aliphatic Nitriles under Mild Conditions [J].

Adam, Rosa ;

Alberico, Elisabetta ;

Baumann, Wolfgang ;

Drexler, Hans-Joachim ;

Jackstell, Ralf ;

Junge, Henrik ;

Beller, Matthias .

CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (14) :4991-5002

[2] Van der Waals radii of elements [J].

Batsanov, SS .

INORGANIC MATERIALS, 2001, 37 (09) :871-885

[3] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[4] (p-cymene)ruthenium(II)(diphenylphosphino)alkyne complexes:: Preparation of (μ-Cl)(μ-PPh2C≡CR)-bridged Ru/Pt heterobimetallic complexes [J].

Berenguer, JR ;

Bernechea, M ;

Forniés, J ;

García, A ;

Lalinde, E .

ORGANOMETALLICS, 2004, 23 (18) :4288-4300

[5]

Braunstein P, 2001, ANGEW CHEM INT EDIT, V40, P680, DOI 10.1002/1521-3773(20010216)40:4<680::AID-ANIE6800>3.0.CO

[6]

2-0

[7] Transition metal complexes containing allenylidene, cumulenylidene, and related ligands [J].

Bruce, MI .

CHEMICAL REVIEWS, 1998, 98 (08) :2797-2858

[8] Metal vinylidenes in catalysis [J].

Bruneau, C ;

Dixneuf, PH .

ACCOUNTS OF CHEMICAL RESEARCH, 1999, 32 (04) :311-323

[9] Efficient Base-Free Hydrogenation of Amides to Alcohols and Amines Catalyzed by Well-Defined Pincer Imidazolyl-Ruthenium Complexes [J].

Cabrero-Antonino, Jose R. ;

Alberico, Elisabetta ;

Drexler, Hans-Joachim ;

Baumann, Wolfgang ;

Junge, Kathrin ;

Junge, Henrik ;

Beller, Matthias .

ACS CATALYSIS, 2016, 6 (01) :47-54

[10]

Cadierno V, 2001, EUR J INORG CHEM, P571

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