630111-11-4Relevant academic research and scientific papers
Donor Properties of a New Class of Guanidinate Ligands Possessing Ketimine Backbones: A Comparative Study Using Iron
Maity, Arnab K.,Metta-Maga?a, Alejandro J.,Fortier, Skye
, p. 10030 - 10041 (2015/11/10)
Addition of 1 equiv of LiN=CtBu2 or LiN=Ad (Ad = 2-adamantyl) to the aryl carbodiimide C(NDipp)2 (Dipp = 2,6-diisopropylphenyl) readily generates the lithium ketimine-guanidinates Li(THF)2[(X)C(NDipp)2] (X = N=CtBu2 (1-tBu), N=Ad (1-Ad)) in excellent yields. These new ligands can be readily metalated with iron to give the N,N′-bidentate chelates [{(X)C(NDipp)2}FeBr]2 (X = N=CtBu2 (5-tBu), N=Ad (5-Ad)), in which the ketimines behave as noncoordinating backbone substituents. In an effort to understand the potential electronic contributions of the ketimine group to the ligand architecture, a thorough structural and electronic study was conducted comparing the features and properties of 5-tBu and 5-Ad to their guanidinate and amidinate analogues [{(X)C(NDipp)2}FeBr]2 (X = iPr2N (6), tBu (7)). Solid-state structural analyses indicate little electronic contribution from the N-ketimine nitrogen atom, while solution-phase electronic absorption spectra of 5-tBu and 5-Ad are qualitatively similar to the amidinate complex 7. Yet, electrochemical measurements do show the donor properties of the ketimine-guanidinate in 5-tBu to be intermediate between its guanidinate and amidinate counterparts in 6 and 7. Preliminary reactivity studies also show that the reduction chemistry of 5-tBu diverges significantly from that of 6 and 7. Treatment of 5-tBu with excess magnesium or 1 equiv of KC8 leads to the formation of the Fe(I)-Fe(I) complex [{μ-(tBu2C=N)C(NDipp)2}2Fe2] (11), which possesses an exceedingly short Fe=Fe bond (2.1516(5) ?), while neither 6 nor 7 forms dinuclear complexes upon reduction. This result demonstrates that ketimine-guanidinates do not simply behave as amidinate variants but can contribute to distinctive metal chemistry of their own.
N,N′-Bis(2,6-diisopropylphenyl)benzamidinates and -pivalamidinates of the s-block metals lithium, potassium, and calcium
Loh, Claas,Seupel, Susanne,G?rls, Helmar,Krieck, Sven,Westerhausen, Matthias
supporting information, p. 1312 - 1321 (2014/04/03)
Metalation of N,N′-bis(2,6-diisopropylphenyl)benzamidine (1a) and -pivalamidine (1b) in tetrahydrofuran (THF) with n-butyllithium and potassium bis(trimethylsilyl)amide gives the corresponding N,N′-bis(2,6- diisopropylphenyl)benzamidinates and -pivalamidi
N,N′-Bis(2,6-diisopropylphenyl)benzamidinates and -pivalamidinates of the s-block metals lithium, potassium, and calcium
Loh, Claas,Seupel, Susanne,G?rls, Helmar,Krieck, Sven,Westerhausen, Matthias
supporting information, p. 1312 - 1321 (2015/04/27)
Metalation of N,N′-bis(2,6-diisopropylphenyl)benzamidine (1a) and -pivalamidine (1b) in tetrahydrofuran (THF) with n-butyllithium and potassium bis(trimethylsilyl)amide gives the corresponding N,N′-bis(2,6-diisopropylphenyl)benzamidinates and -pivalamidin
Synthesis and structural characterization of new zinc amidinate complexes
Schmidt, Sarah,Schulz, Stephan,Blaeser, Dieter,Boese, Roland,Bolte, Michael
experimental part, p. 6097 - 6103 (2011/02/27)
The synthesis and reactivity of heteroleptic zinc complexes of the type LZnX (X = Me, I) containing amidinate ligands L of varying steric bulk were investigated. Complexes of the type LZnMe, which were obtained from the homoleptic complexes L2Z
Synthesis, structure, and properties of magnesium complexes containing cyclopentadienyl and amidinate ligand sets
Xia, Aibing,El-Kaderi, Hani M.,Heeg, Mary Jane,Winter, Charles H.
, p. 224 - 232 (2007/10/03)
N,N′-Bis(2,6-diisopropylphenyl)(tert-butyl)amidine and N,N′-bis(2,4,6-trimethyl-phenyl)(tert-butyl)amidine were prepared and treated with [CpMgMe(Et2O)]2 in diethyl ether or tetrahydrofuran to afford the monomeric amidinate complexes
