Reactivity with Amines of Bis(cyanamide) and Bis(cyanoguanidine) Complexes of the Iron Triad

Albertin, Gabriele; Antoniutti, Stefano; Caia, Alfonso; Castro, Jesús

doi:10.1002/zaac.201400591

Cited by 8 publications

(1 citation statement)

References 55 publications

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“…Albertin et al initiated a program to study the behavior of amino substituted nitriles, such as cyanamides and cyanaoguanidines, and their coordination chemistry with metals like iron, ruthenium and osmium [ 75 , 76 ]. The bivalent metallic bis-cyanamide complex of iron 161 was obtained by mixing FeCl 2 with P(OEt) 3 and then treating with dialkyl-cyanamide followed by addition of an excess of NaBPh 4 ( Scheme 32 A).…”

Section: Synthetic Applications Of Substituted Cyanamidesmentioning

confidence: 99%

Recent Advances in Cyanamide Chemistry: Synthesis and Applications

et al. 2017

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Section: Synthetic Applications Of Substituted Cyanamidesmentioning

confidence: 99%

Recent Advances in Cyanamide Chemistry: Synthesis and Applications

et al. 2017

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Highly Reactive Ni^II‐Bound Nitrile–Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide

et al. 2015

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Nickel(II)‐mediated coupling between the cyanamide Me2NCN and the ketoximes Me(R)C=NOH (R = Me, Ph) gives chelates of the general formula [NiClx(H2O)y{HN=C(NMe2)(ON=C(R)Me)}2]n+ ([1]+: R = Me; x = 1, y = 0; salts with both Cl– and [NiCl4]2– were isolated; [2]2+: R = Me; x = 0, y = 2; salt with Cl– was isolated; [3]+: R = Ph; x = 1, y = 1; salt with Cl– was isolated) and the iminium salts [H2N=C(NMe2)ON=C(R)Me]+ ([4]+: R = Me; salt with [NiCl4]2– was isolated; [5]+: R = Ph; salt with Cl– was isolated). This reaction demonstrates the difference in the reactivity between conventional nitriles and dialkylcyanamides: whereas nitriles RCN (R = Alk, Ar) react with NiII/ketoxime systems to afford (1,3,5‐triazapentadiene)NiII species, formed by postulated nitrile–oxime coupling intermediates, cyanamides under the same conditions give either stable cyanamide–oxime coupling products or the Busch‐type complex [Ni{HN=C(Me)CH2C(Me2)NH2}2]Cl2 ([6]Cl2). The reason for the different stability of the coupling products was interpreted theoretically on the basis of quantum chemical calculations (M06‐L/6‐31G* level of theory). The NMe2 moiety in the chelate ligands leads to an increase in electron‐density delocalization and also stabilizes the systems in terms of electrostatic factors.

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Preparation of Diethylcyanamide and Cyanoguanidine Complexes of Iridium

2018

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Diethylcyanamide [IrCl(η5‐C5Me5)(N≡CNEt2){P(OR)3}]BPh4 (1) and cyanoguanidine complexes [IrCl(η5‐C5Me5){N≡CN(H)C(NH2)=NH}{P(OR)3}]BPh4 (2) were prepared by allowing chloro compounds [IrCl2(η5‐C5Me5){P(OR)3}] to react with an excess of cyanamide or cyanoguanidine, respectively. Alternatively, complexes 2 were prepared by reacting [IrCl2(η5‐C5Me5){P(OR)3}] with an excess of cyanamide N≡CNH2. Bis(diethylcyanamide) [Ir(η5‐C5Me5) (N≡CNEt2)2{P(OR)3}](BPh4)2 (3) and bis(cyanoguanidine) derivatives [Ir(η5‐C5Me5){N≡CN=C(NH2)2}2{P(OR)3}](BPh4)2 (4) were also prepared by treating dichloro precursors [IrCl2(η5‐C5Me5){P(OR)3}] first with two equivalents of AgOTf and then with an excess of diethylcyanamide or cyanoguanidine, respectively. The compounds were characterised spectroscopically (IR and NMR) and by X‐ray crystal structure determination of [Ir(η5‐C5Me5)(N≡CNEt2)2{P(OMe)3}](BPh4)2.

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Reactivity with Amines of Bis(cyanamide) and Bis(cyanoguanidine) Complexes of the Iron Triad

Cited by 8 publications

References 55 publications

Recent Advances in Cyanamide Chemistry: Synthesis and Applications

Recent Advances in Cyanamide Chemistry: Synthesis and Applications

Highly Reactive Ni^II‐Bound Nitrile–Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide

Preparation of Diethylcyanamide and Cyanoguanidine Complexes of Iridium

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Reactivity with Amines of Bis(cyanamide) and Bis(cyanoguanidine) Complexes of the Iron Triad

Cited by 8 publications

References 55 publications

Recent Advances in Cyanamide Chemistry: Synthesis and Applications

Recent Advances in Cyanamide Chemistry: Synthesis and Applications

Highly Reactive NiII‐Bound Nitrile–Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide

Preparation of Diethylcyanamide and Cyanoguanidine Complexes of Iridium

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Highly Reactive Ni^II‐Bound Nitrile–Oxime Coupling Intermediates Stabilized by Substituting Conventional Nitriles with a Dialkylcyanamide