Reactivity of a Co(i) [N2P2] complex with azides: evidence for a transient Co(iii) imido species

Chomitz, Wayne A.; Arnold, John

doi:10.1039/b804754e

Cited by 32 publications

(23 citation statements)

References 32 publications

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“…14 Our group has a long time interest in using potentially reactive metal-carbon bonds toward small molecule activation. [15][16][17][18][19][20][21] We recently reported the use of Tp Ph,Me in stabilizing reactive Co-alkyl complexes, which were found to undergo intramolecular isomerization upon homolytic bond cleavage. 22 In attempt to extend this chemistry to other late first row transition metals, we herein report the synthesis of alkyl manganese(II) and nickel(II) supported by the Tp Ph,Me ligand, along with cobalt(II) and nickel(II) azide complexes.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

et al. 2013

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The synthesis of several nickel(II) and manganese(II) alkyl complexes supported by hydrotris(3-phenyl-5-methylpyrazolyl)borate (Tp(Ph,Me)) ligand is reported. The metal halide complexes Tp(Ph,Me)MnCl(CH3CN) (1) and Tp(Ph,Me)NiCl (4) were used as precursors for synthesis of Tp(Ph,Me)MnCH2Si(Me)3 (2), Tp(Ph,Me)MnCH2Ph (3), Tp(Ph,Me)NiCH2Si(Me)3 (5) and Tp(Ph,Me)NiCH2Ph (6). The resulting Mn(II) and Ni(II) alkyl complexes, 2-3 and 5-6, were characterized by X-ray crystallography, NMR spectroscopy, and FT-IR spectroscopy. X-ray crystallographic analysis revealed distorted tetrahedral geometries for complexes 2-3 and 5 with a κ(3)-Tp(Ph,Me). Complex 6, on the other hand, was found to have a distorted square planar geometry with κ(2)-Tp(Ph,Me) and an η(3)-benzyl ligand. Transformations of 4 and Tp(Ph,Me)CoCl (10) via treatment with NaN3 to yield Tp(Ph,Me)NiN3 (11), Tp(Ph,Me)CoN3 (12), along with the synthesis of (Tp(Ph,Me))2Ni (8) and Tp(Ph,Me)NiCl(3-Ph-5MepzH) (9) are also reported.

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Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

et al. 2013

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“…The reduction chemistry of selected complexes supported by the N 2 P 2 ligand was explored and resulted in the isolation of the new bridging dinitrogen complexes (Figure 15). [64,65]…”

Section: "Mixed-donor" Tripodal Ligandsmentioning

confidence: 99%

“…The reduction chemistry of selected complexes supported by the N 2 P 2 ligand was explored and resulted in the isolation of the new bridging dinitrogen complexes [{TiCl(N 2 P 2 )} 2 (μ‐N 2 )], [{Mn(N 2 P 2 )} 2 (μ‐N 2 )], and [{Fe(N 2 P 2 )} 2 (μ‐N 2 )] as well as the low‐valent monomeric Co I species [Co(N 2 P 2 )] (Figure 15). 64, 65 Alkylation of [{TiCl(N 2 P 2 )} 2 (μ‐N 2 )]with two equivalents of LiCH 2 SiMe 3 led to the isolation of the bis‐alkyl bridging dinitrogen complex [{TiCH 2 SiMe 3 (N 2 P 2 )} 2 (μ‐N 2 )] and was the first alkylation of a bridging dinitrogen complex reported. The NN bond length in [{Mn(N 2 P 2 )} 2 (μ‐N 2 )] (1.208(6) Å) is significantly longer than the NN distance observed in the only other previously known example of a bridging N 2 complex of Mn, [{Mn(η 5 ‐C 5 H 4 CH 3 )(CO) 2 } 2 (μ‐N 2 )] (1.118(7) Å).…”

Section: “Mixed‐donor” Tripodal Ligandsmentioning

confidence: 99%

Use of Tetradentate Monoanionic Ligands for Stabilizing Reactive Metal Complexes

Chomitz¹,

Arnold²

2009

Chemistry A European J

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Ligand scaffolding: The chemist's ability to choose from a wide range of supporting ligands is an important factor in designing new metal complexes. The introduction of new ligand scaffolds with different donor types and coordination numbers allows for the expansion of reaction chemistry at metal centers. This article surveys the use of the tetradentate monoanionic (TMDA) ligands (shown here) with main-group, transition-metal, and f-block elements. Supporting ligand design has played a vital role in the development of coordination and organometallic chemistry. A myriad of ligands with varying charge, donor-type, and denticity have been explored in this realm. A ligand type that has garnered recent attention involves a tetradentate monoanionic (TDMA) framework. TDMA ligands have been used with p-, d-, and f-block elements to form an array of interesting new complexes with applications ranging from bioinorganic chemistry to catalysis. Complexes incorporating TDMA ligands have been shown to stabilize reactive low-valent and cationic species. Functionalized beta-diiminato and TACN derivatives as well as tripodal ligands featuring both hard sigma-donors as well as "mixed-donors" are covered in this review. The synthetic challenges associated with the implementation of each ligand set are discussed.

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“…The fourcoordinate iodo complex 22 was obtained as dark green blocks in 83% yield and shown to adopt a distorted tetrahedral arrangement with the ligand in a P 2 N-ligating mode. 16 Reaction of 22 with K[C 8 ] in THF gave 23 which, from single crystal XRD, revealed a P 2 N 2 ligand coordination mode at a low valent Co(I) metal centre. The Co(II) complex 24 (R = Ph) was synthesised and characterised.…”

Section: Cobalt Chemistrymentioning

confidence: 99%

Cobalt, rhodium and iridium

Smith

2009

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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This chapter provides a selective review of the literature for 2008 on the chemistry of the Group 9 elements. HighlightsThe year 2008 has witnessed some remarkable work in the field of Co, Rh and Ir chemistry. Some notable highlights include the synthesis and structural characterisation of a unique heterobimetallic Co/Pt complex, 14 a highly active Co catalyst for O 2 generation from water, 26 new Z 2 -amine-borane s-complexes of Rh(I), 30 cationic Ir(III) complexes as phosphorescent dyes for living cell imaging 74 and H/D exchange reactions catalysed by Ir complexes. 88,89

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Reactivity of a Co(i) [N2P2] complex with azides: evidence for a transient Co(iii) imido species

Abstract: The synthesis of a monomeric Co(i) complex supported by a multidentate monoanionic [N(2)P(2)] ligand is described; interaction with aryl azides at low temperature generates a species whose reactivity is consistent with imido ("Co[double bond, length as m-dash]NR") character.

Cited by 32 publications

References 32 publications

Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

Synthesis and characterization of coordinatively unsaturated nickel(ii) and manganese(ii) alkyl complexes supported by the hydrotris(3-phenyl-5-methylpyrazolyl)borate (TpPh,Me) ligand

Use of Tetradentate Monoanionic Ligands for Stabilizing Reactive Metal Complexes

Cobalt, rhodium and iridium

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