Redox-Coupled Complexation of 23-Phospha-21-thiaporphyrin with Group 10 Metals: A Convenient Access to Stable Core-Modified Isophlorin−Metal Complexes

2008 ◽  
Vol 130 (49) ◽  
pp. 16446-16447 ◽  
Author(s):  
Yoshihiro Matano ◽  
Takashi Nakabuchi ◽  
Shinya Fujishige ◽  
Haruyuki Nakano ◽  
Hiroshi Imahori
Keyword(s):  
Metal Complexes ◽  
Stable Core ◽  
Group 10 ◽  
Group 10 Metals ◽  
Convenient Access

scholarly journals Synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes

2010 ◽  
Vol 82 (3) ◽  
pp. 583-593 ◽  
Author(s):  
Yoshihiro Matano ◽  
Takashi Nakabuchi ◽  
Hiroshi Imahori
Keyword(s):  
Structural Analysis ◽  
Metal Complexes ◽  
Phosphorus Atom ◽  
Porphyrin Ring ◽  
Free Base ◽  
X Ray ◽  
The Core ◽  
Group 10 ◽  
Group 10 Metals ◽  
Theoretical Results

Our recent studies on the synthesis, structures, and aromaticity of phosphole-containing porphyrins and their metal complexes are summarized. Core-modified P,X,N2-porphyrins (X = S, N) are accessible from a σ4-phosphatripyrrane and the corresponding 2,5-difunctionalized heteroles in a few steps. X-ray structural analysis of the σ3-P,N3 porphyrin revealed that it possesses a slightly distorted 18π plane. The phosphorus atom incorporated at the core plays an important role in producing unprecedented reactivity and coordinating ability for the porphyrin ring. The P,N3 free base reacts with [RhCl(CO)2]2 in dichloromethane, ultimately yielding an 18π P,N3–rhodium(III) complex, whereas the P,S,N2 free base undergoes redox-coupled complexation with zero valent group 10 metals to afford the corresponding P,S,N2-isophlorin–metal(II) complexes. The aromaticity of the free-base porphyrins and the metal complexes was uncovered based on both experimental and theoretical results. It is of particular interest that the P,S,N2-isophlorin–metal complexes exhibit only a weak antiaromaticity in terms of the magnetic criterion.

Zero-valent ML2 complexes of group 10 metals supported by terphenyl phosphanes

2021 ◽  
Author(s):  
M. Trinidad Martín ◽  
Mario Marín ◽  
Raquel J. Rama ◽  
Eleuterio Alvarez González ◽  
Celia Maya ◽  
...  
Keyword(s):  
Coordination Numbers ◽  
Group 10 ◽  
Group 10 Metals

Bulky terphenyl phosphane ligands PMe2Ar’ (Ar’ = terphenyl group) facilitate the isolation of zero-valent bis-phosphane complexes of nickel, palladium and platinum. The former show coordination numbers greater than two in...

Toward Butadiene-ATRP with Group 10 (Ni, Pd, Pt) Metal Complexes

2018 ◽  
pp. 205-225 ◽  
Author(s):  
Vignesh Vasu ◽  
Joon-Sung Kim ◽  
Hyun-Seok Yu ◽  
William I. Bannerman ◽  
Mark E. Johnson ◽  
...  
Keyword(s):  
Metal Complexes ◽  
Group 10

A convenient access to N-phosphonio-substituted NHC metal complexes [M = Ag(i), Rh(i), Pd(ii)]

2017 ◽  
Vol 46 (36) ◽  
pp. 12293-12305 ◽  
Author(s):  
Idir Benaissa ◽  
Rachid Taakili ◽  
Noël Lugan ◽  
Yves Canac
Keyword(s):  
Metal Complexes ◽  
Metal Center ◽  
Convenient Access

NHC Pd(ii) complexes featuring a propyl bridge were ionized by the introduction of a phosphonium moiety, which may coordinate to the metal center or remain pendant.

scholarly journals Synthesis and Reactivity of Group 10 Transition Metal Complexes with Alkenylphosphoryl Compounds

2019 ◽  
Vol 39 (8) ◽  
pp. 2183
Author(s):  
Tieqiao Chen ◽  
Long Liu ◽  
Tianzeng Huang ◽  
Li-Biao Han
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Group 10

scholarly journals DFT-Assisted Design and Evaluation of Bifunctional Amine/Pyridine-Oxazoline Metal Catalysts for Additions of Ketones to Unactivated Alkenes and Alkynes

Synthesis ◽  
2018 ◽  
Vol 51 (02) ◽  
pp. 450-462 ◽  
Author(s):  
Chris Dockendorff ◽  
Eric Greve ◽  
Jacob Porter
Keyword(s):  
Density Functional ◽  
Bond Formation ◽  
Bifunctional Catalyst ◽  
Catalyst Design ◽  
Epoxide Ring ◽  
Nmr Studies ◽  
Acidic Group ◽  
Direct Addition ◽  
Group 10 ◽  
Group 10 Metals

Bifunctional catalyst systems for the direct addition of ­ketones to unactivated alkenes/alkynes were designed and modeled by density functional theory (DFT). The designed catalysts possess bidentate ligands suitable for binding of pi-acidic group 10 metals capable of activating alkenes/alkynes, and a tethered organocatalyst amine to ­activate the ketone via formation of a nucleophilic enamine intermediate. The structures of the designed catalysts before and after C–C bond formation were optimized using DFT, and reaction steps involving group 10 metals were predicted to be significantly exergonic. A novel oxazoline precatalyst with a tethered amine separated by a meta-substituted benzene spacer was synthesized via a 10-step sequence that ­includes a key regioselective epoxide ring-opening step. It was combined with group 10 metal salts, including cationic Pd(II) and Pt(II), and screened for the direct addition of ketones to several alkenes and an ­internal alkyne. 1H NMR studies suggest that catalyst-catalyst inter­actions with this system via amine–metal coordination may preclude the desired addition reactions. The catalyst design approach disclosed here, and the promising calculations obtained with square planar group 10 metals, light a path for the discovery of novel bifunctional catalysts for C–C bond formation.

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