Synthesis and reactivity of bis(diphenylphosphino)amine-bridged heterobimetallic iron–platinum μ-isonitrile and μ-aminocarbyne complexes

Knorr, Michael; Jourdain, Isabelle; Mohamed, Ahmed Said; Khatyr, Abderrahim; Koller, Stephan G.; Strohmann, Carsten

doi:10.1016/j.jorganchem.2014.12.028

Cited by 16 publications

(8 citation statements)

References 78 publications

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“…The full NMR spectroscopic characterization of the already known 1a – c is supplied here for the first time. The carbyne nature of the bridging [CN] moiety in 1a – e is manifested by a strongly deshielded 13 C NMR spectroscopic resonance (e.g., at δ = 327.8 ppm in the case of 1c in CDCl 3 solution) , . Compound 1d exists in solution as two isomeric forms in a comparable ratio, the two isomers presumably differing in the orientation of the aryl‐substituents (i.e., Me and Cl) with respect to the Fe–Fe axis.…”

Section: Resultsmentioning

confidence: 99%

Regioselective Nucleophilic Additions to Diiron Carbonyl Complexes Containing a Bridging Aminocarbyne Ligand: A Synthetic, Crystallographic and DFT Study

et al. 2017

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Diiron μ-aminocarbyne compounds, 1a-e, are prepared in two steps from Fe 2 Cp 2 (CO) 4 , negating the need for difficult purification procedures of intermediate species; they are efficiently isolated by alumina chromatography. Minor amounts of μ-aminocarbyne aryl isocyanide compounds, 2a-c, are obtained as side products. The structures of the cations in 1a,c,e are calculated using DFT; the carbyne carbon is generally predicted to be the thermodynamic site of hydride addition, in agreement with a previous experimental finding concerning 1a. Accordingly, the reaction of 1e with NaBH 4 affords a bridging aminocarbene complex, 4, in 85 % yield. Otherwise, the reaction of 1c with NaBH 4 yields the aminocarbyne-cyclopentadiene derivative 3 (70 %), presumably as a consequence of the [a] Scheme 1. Regioselective additions of nucleophiles to the diiron aminocarbyne complex 1a. Results and DiscussionThe commercial compound [Fe 2 Cp 2 (CO) 4 ] was reacted with the appropriate isocyanide, in a ca. 3:2 molar ratio, in acetonitrile solution. [16] The reactions with alkyl isocyanides were conducted under reflux conditions, whereas the reactions with aryl isocyanides proceeded at room temperature. The resulting mixtures were dried under vacuum and the residues were dissolved in dichloromethane and then treated with methyl triflate, thus affording the μ-aminocarbyne complexes 1a-e (Scheme 2). The difficult isolation of the monoisocyanide intermediates (see the Introduction) was unnecessary. The final products 1a-e were efficiently purified by alumina chromatography and were then isolated as microcrystalline, air-stable compounds in 65-92 % yields. The synthesis of 1c-e was accompanied by the side formation of minor products derived from di-isocyanide species, 2a-c. Compounds 2a-c were recovered by the chromatography in 3-12 % yields, although 2a was formerly reported as being Scheme 2. Synthesis of diiron μ-aminocarbyne complexes.Eur. J. Inorg. Chem. 2018, 960-971 www.eurjic.org

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Section: Resultsmentioning

confidence: 99%

Regioselective Nucleophilic Additions to Diiron Carbonyl Complexes Containing a Bridging Aminocarbyne Ligand: A Synthetic, Crystallographic and DFT Study

et al. 2017

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“…More recently, Knorr and colleagues studied the reactivity of bis(diphenylphosphino)amine-bridged heterobimetallic iron–platinum μ-aminocarbyne complexes and isolated the hetero-trimetallic complexes 398 – 403 , which resulted from the clean reaction of the zwitterionic precursor complex 397 with [ML′]X (M = Au, Cu; L′ = PPh 3 , AsPh 3 ; X = CF 3 SO 3 , NO 3 ) or MeHgCl reagents (Scheme ). Complexes 398 – 403 exhibit typical and similar patterns in their 31 P NMR spectra, owing to the nonequivalent P atoms of the DPPA-type ligand and numerous J P,P and J P,Pt couplings. This results for 398 in doublets of doublets of doublets (ddd) at δ 105.6 (P1), 87.0 (P2) ppm for the DPPA-type ligand (Scheme , Table ), and its spectrum contains also a signal at 34.8 (ddd, P3) ppm for the Pt–PPh 3 phosphine and at 32.3 (q) ppm for the Au–PPh 3 phosphine.…”

Section: N-metal Functionalizationsmentioning

confidence: 99%

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

2016

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The aim of this review is to highlight how the diversity generated by N-substitution in the well-known short-bite ligand bis(diphenylphosphino)amine (DPPA) allows a fine-tuning of the ligand properties and offers a considerable scope for tailoring the properties and applications of their corresponding metal complexes. The various N-substituents include nitrogen-, oxygen-, phosphorus-, sulfur-, halogen-, and silicon-based functionalities and directly N-bound metals. Multiple DPPA-type ligands linked through an organic spacer and N-functionalized DRPA-type ligands, in which the PPh2 substituents are replaced by PR2 (R = alkyl, benzyl) groups, are also discussed. Owing to the considerable diversity of N-functionalized DPPA-type ligands available, the applications of their mono- and polynuclear metal complexes are very diverse and range from homogeneous catalysis with well-defined or in situ generated (pre)catalysts to heterogeneous catalysis and materials science. In particular, sustained interest for DPPA-type ligands has been motivated, at least in part, by their ability to promote selective ethylene tri- or tetramerization in combination with chromium. Ligands and metal complexes where the N-substituent is a pure hydrocarbon group (as opposed to N-functionalization) are outside the scope of this review. However, when possible, a comparison between the catalytic performances of N-functionalized systems with those of their N-substituted analogs will be provided.

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“…Analogous bis‐aminoalkylidyne species were also reported in the past . On the other hand, stable polynuclear compounds with bridging aminoalkylidyne ligands are relatively rare in the literature, based on molybdenum, nickel, tungsten, platinum, iron and heterodinuclear systems, and their chemistry has been sparingly developed.…”

Section: Introductionmentioning

confidence: 99%

Constructing Organometallic Architectures from Aminoalkylidyne Diiron Complexes

Marchetti

2018

Eur J Inorg Chem

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The chemistry of diiron complexes has seen a recent renaissance, due to the prominent role played by the element iron in the development of sustainable synthetic processes and the cooperative effects provided by two metal centers working in concert, that is a concept amazingly exploited by Nature. Aminoalkylidyne derivatives of [Fe 2 Cp 2 (CO) 4 ] are a convenient scaffold to grow organic fragments; in particular, the facile re-[a] received his PhD degree in Chemistry from the University of Bologna in 2003, then he moved to the University of Pisa in 2006, where he is currently Professor of Inorganic Chemistry. He has co-authored over 150 papers in international journals, dealing with several aspects of the coordination chemistry of transition metal compounds. He was awarded the Nasini Prize by the Italian Chemical Society in 2014, for his contribution to the chemistry of group 5 and 6 metal compounds and to the exploration of unconventional modes of metal mediated C-C bond formation. 3990 Scheme 7. Coupling of isocyanide ligands promoted by acetylide addition to aminoalkylidyne complexes. (a) R = Xyl, R′ = Ph; R = Xyl, R′ = 4-C 6 H 4 Me; R = Me, R′ = Ph. (b) γ-Al 2 O 3 , R′ = SiMe 3 . [51]Eur. 3991Scheme 8. Base-assisted coupling of aminoalkylidyne ligand (R = Me, Xyl or 4-C 6 H 4 OMe) with (a) alkenes (R′ = H, R′′ = CN, CO 2 Me, Ph; R′ = R′′ = CO 2 Et) [53] and (b) allenes (R′ = R′′ = Me; R′ = Me, CO 2 Et, R′′ = H). [54] Scheme 9. Synthesis of vinyliminium complexes via alkyne insertion into Fe-μ-carbyne bond. Inset: possible forms of isomerism. [61][62][63] Eur.

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Synthesis and reactivity of bis(diphenylphosphino)amine-bridged heterobimetallic iron–platinum μ-isonitrile and μ-aminocarbyne complexes

Cited by 16 publications

References 78 publications

Regioselective Nucleophilic Additions to Diiron Carbonyl Complexes Containing a Bridging Aminocarbyne Ligand: A Synthetic, Crystallographic and DFT Study

Regioselective Nucleophilic Additions to Diiron Carbonyl Complexes Containing a Bridging Aminocarbyne Ligand: A Synthetic, Crystallographic and DFT Study

Functional Short-Bite Ligands: Synthesis, Coordination Chemistry, and Applications of N-Functionalized Bis(diaryl/dialkylphosphino)amine-type Ligands

Constructing Organometallic Architectures from Aminoalkylidyne Diiron Complexes

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