Synthesis and Characterization of a Linear, Two-Coordinate Pt(II) Ketimide Complex

Cook, Andrew W.; Hrobárik, Peter; Damon, Peter L.; Najera, Daniel; Horváth, Branislav; Hayton, Trevor W.

doi:10.1021/acs.inorgchem.9b02443

Cited by 13 publications

(18 citation statements)

References 66 publications

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“…The approximately linear N-Pt-N axis is maintained (N-Pt-N angle: 176.0(4)°) and slight elongation of the Pt-N PNP bond (Δd = 0.06 Å) indicates increased trans influence. In turn, the distance to the atomic nitrogen ligand (d Pt-N = 1.874(11) Å) is at the lower end of experimentally observed Pt-N bond lengths 35 and significantly shortened with respect to 1 (Pt-N 3 distance: 2.031(5) Å) or an independently prepared parent amide complex (Pt(NH 2 )(PNP)) (3; Pt-NH 2 distance: 2.030(3) Å). A similar bond length (1.81 Å) was computed for the Pt=O core in Milstein's platinum oxo complex 36,37 .…”

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confidence: 90%

A platinum(ii) metallonitrene with a triplet ground state

et al. 2020

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ational synthetic method development is driven by the ability to relate reactivity to the electronic structures of key transient intermediates. For example, organic nitrenes (R-N) are generally highly reactive monovalent nitrogen species and detailed spectroscopic studies have enabled the assignment of their diverse reaction pathways, such as C-H insertion or N-N coupling, to the accessibility of triplet versus (open shell) singlet spin states 1,2 . In comparison, the well-established class of nitrido complexes (L n MN) commonly features trivalent nitrogen with significant covalent components of M-N σand π-bonding (Fig. 1a) 3 . Increased radical and electrophilic nitrogen character can be formally represented by divalent nitridyl all the way to monovalent metallonitrene contributions 4 . Formal nitrido complexes with predominant subvalent metallonitrene (L n M-N) character, which can be regarded as metal analogues of organic nitrenes, have been proposed as key intermediates in stoichiometric intramolecular [5][6][7][8][9] and intermolecular 10-15 nitrogen atom transfer reactions. However, in contrast to organic nitrenes 16 , authentic metallonitrenes with a monovalent atomic nitrogen ligand remain elusive, which impedes the development of new nitrogen transfer reactions based on electronic structure/reactivity relationships.The emergence of C-H amination and amidation via nitrene transfer as a powerful synthetic tool was fuelled by the development of group 9-11 transition metal catalysts that facilitate selective insertion of coordinated nitrene fragments (Fig. 1b) [17][18][19] . Late transition metals are also instrumental as anode materials in electrocatalytic amine oxidation for synthetic and fuel cell applications [20][21][22] . The dominance of late transition metals in redox transformations of nitrogenous species stimulated fundamental interest in M-N(R) bonding 3 . C-H insertion by L n M-NR species has been associated with electrophilic subvalent nitrene ( 3 NR) 23 or imidyl ( 2 NR − ) [24][25][26] character that arises from low lying d orbitals of late transition met-als. This strongly reduces the imido ( 1 NR 2− ) contribution 27,28 . Similar considerations might apply for metallonitrene (L n M-N) or nitridyl (L n M=N • ) versus nitrido (L n M≡N) species (Fig. 1a). However, intermolecular C-H activation has not been reported for the few known late transition metal nitrido or nitridyl complexes [29][30][31] . The exploitation of nitrogen atom insertion reactivity (Fig. 1b) is still in its infancy; as of yet, catalytic protocols are not known and systematic advances suffer from the lack of well-defined metallonitrene platforms.In this contribution, a formal nitrido complex beyond group 9 is reported. Crystallographic, spectroscopic, magnetic and computational characterization shows a triplet electronic ground state with a predominantly single-bonded metallonitrene (L n Pt ii -N) and nitrogen-centred diradical character. Facile N-atom insertion into C-H, B-H and B-C bonds is demonstrated. In contrast to the...

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A platinum(ii) metallonitrene with a triplet ground state

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“…Note, while Hillhouse's linear nickel(II) imido complexes exhibits a triplet ground state, ( cf . Figure 7), [11] a diamagnetic ground state was found for 46 [99] …”

Section: Group 10 Metalsmentioning

confidence: 90%

“…Formal multiple bonds with platinum are exceedingly rare [98] . In 2019, the platinum(II) complex 47 with two ketimide ligands was isolated [99] . It represents not only the first linear two‐coordinated platinum(II) complex, but also shows remarkable short Pt−N bonds of 1.815(4) Å and 1.818(4) Å (Figure 25).…”

Section: Group 10 Metalsmentioning

confidence: 99%

Terminal Imido Complexes of the Groups 9–11: Electronic Structure and Developments in the Last Decade

2021

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“…The imine N atom can act as a monodentate or A simple ketimine ligand may yield complexes coordinated in the κ 1 -N monodentate mode. An example is a binuclear complex of Pt with additional activated 1,5-cyclooctadiene fragment acting as a bridge between two metal centers (Figure 3a; MOYJES) [113]. Secondary ketimine ligands were also utilized as monodentate ligands supplementing the coordination sphere in complexes of Rh [114] and Pd [115].…”

Section: Imine As a Monodentate And Bridging Ligandmentioning

confidence: 99%

“…Secondary ketimine ligands were also utilized as monodentate ligands supplementing the coordination sphere in complexes of Rh [114] and Pd [115]. [113] (CSD Refcode MOYJES); (b) binuclear complex of Ir(II) with ketimine as an intermetallic bridge and 1,5-cyclooctadiene ligands located on the outside of the coordination unit [116] (CSD Refcode KABLOP); (c) bridging µ 2 -κ 2 ethanimine ligand in metallaborane tetra-ruthenium cluster with boron-nitrogen coupling [117] (CSD Refcode PORSUK); (d) binuclear complex of Rh(II) with ketimine bridging ligand [118], shown only one symmetrically independent molecule (CSD Refcode LIFMIW); (e) heterobimetallic Zr/Pd complex with ketimine linkage [119] (CSD Refcode WAGHOC) and (f) binuclear complex of Pt(II) stabilized by ketimine ligand with very short Pt-Pt distance and activated C-H bond [113] (CSD Refcode MOYHUG). Solvent molecules and hydrogen atoms were omitted for clarity.…”

Section: Imine As a Monodentate And Bridging Ligandmentioning

confidence: 99%

Homo- and Hetero-Oligonuclear Complexes of Platinum Group Metals (PGM) Coordinated by Imine Schiff Base Ligands

Mirosław

2020

IJMS

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Chemistry of Schiff base (SB) ligands began in 1864 due to the discovery made by Hugo Schiff (Schiff, H., Justus Liebigs Ann. der Chemie 1864, 131 (1), 118–119). However, there is still a vivid interest in coordination compounds based on imine ligands. The aim of this paper is to review the most recent concepts on construction of homo- and hetero-oligonuclear Schiff base coordination compounds narrowed down to the less frequently considered complexes of platinum group metals (PGM). The combination of SB and PGM in oligonuclear entities has several advantages over mononuclear or polynuclear species. Such complexes usually exhibit better electroluminescent, magnetic and/or catalytic properties than mononuclear ones due to intermetallic interactions and frequently have better solubility than polymers. Various construction strategies of oligodentate imine ligands for coordination of PGM are surveyed including simple imine ligands, non-innocent 1,2-diimines, chelating imine systems with additional N/O/S atoms, classic N2O2-compartmental Schiff bases and their modifications resulting in acyclic fused ligands, macrocycles such as calixsalens, metallohelical structures, nano-sized molecular wheels and hybrid materials incorporating mesoionic species. Co-crystallization and formation of metallophilic interactions to extend the mononuclear entities up to oligonuclear coordination species are also discussed.

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Synthesis and Characterization of a Linear, Two-Coordinate Pt(II) Ketimide Complex

Cited by 13 publications

References 66 publications

A platinum(ii) metallonitrene with a triplet ground state

A platinum(ii) metallonitrene with a triplet ground state

Terminal Imido Complexes of the Groups 9–11: Electronic Structure and Developments in the Last Decade

Homo- and Hetero-Oligonuclear Complexes of Platinum Group Metals (PGM) Coordinated by Imine Schiff Base Ligands

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