2003
DOI: 10.1021/ic034328f
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Volatile β-Ketoiminato- and β-Diketiminato-Based Zirconium Complexes as Potential MOCVD Precursors

Abstract: An amine elimination pathway has been used to produce a number of homo- and heteroleptic zirconium complexes, starting from tetrakis(dialkylamido)zirconium complexes and beta-diketimine or, alternatively, Schiff Base compounds. Reaction of 2 equiv of the bidentate beta-diketimine (2Z,4E)-N-methyl-4-(methylimino)pent-2-en-2-amine with Zr(NR(2))(4) (R = Me, Et) affords the six-coordinate heteroleptic compounds bis(N-methyl-4-(methylimino)pent-2-en-2-amido)bis(dialkylamido)zirconium 1 (alkyl = Me) and 2 (alkyl = … Show more

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Cited by 52 publications
(38 citation statements)
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“…Despite the boat-like distortion of the ligand in 2a, its bonding mode is essentially a j 2 -, in-plane coordination. Similar coordination modes have been observed for nacnac dipp ZrCl 3 (dipp = 2,6-diisopropylphenyl) [5] and other diketiminato zirconium complexes [3][4][5][6][7]9]. Despite the unsaturation of the zirconium center, nacnac dipp ZrCl 3 displays a long, non-coordinative distance of 3.4 Å between Zr and the C3 atom of the carbon back-bone.…”
supporting
confidence: 65%
See 1 more Smart Citation
“…Despite the boat-like distortion of the ligand in 2a, its bonding mode is essentially a j 2 -, in-plane coordination. Similar coordination modes have been observed for nacnac dipp ZrCl 3 (dipp = 2,6-diisopropylphenyl) [5] and other diketiminato zirconium complexes [3][4][5][6][7]9]. Despite the unsaturation of the zirconium center, nacnac dipp ZrCl 3 displays a long, non-coordinative distance of 3.4 Å between Zr and the C3 atom of the carbon back-bone.…”
supporting
confidence: 65%
“…In mono- [2][3][4][5][6][7][8][9] and bis(diketiminate) complexes of zirconium [4,6,7,10], as well as in complexes with the related iminomethylaniline [11,12] or azaallylpyridine ligands [13,14], the ligand is bound via the two nitrogen lone pairs with the metal found in the ligand mean plane (Scheme 1, A). Steric crowding around the metal center, in particular with sterically demanding substituents on nitrogen, results in a displacement of the metal out of the ligand mean plane (Scheme 1, B) [1,3].…”
mentioning
confidence: 99%
“…For comparable coordination of the nacnac ligand in five-coordinated complexes, see Basuli et al (2004) [Cambridge Structural Database (Allen, 2002) refcodes FAPBUU, FAPCAP, FAPCEF and FABCIJ]. For Zr complexes containing 2 -coordinated nacnac, see: Kakaliou et al (1999); Qian et al (1999); Jin & Novak (2000); Franceschini et al (2003); Hamaki et al (2006). For Zr complexes containing 5 -like coordinated nacnac, see: Rahim et al (1998); Vollmerhaus et al (2000).…”
Section: Related Literaturementioning
confidence: 99%
“…, the N-methyl analog is unstable at room temperature [46]. This structural anomaly is rationalized by in situ rearrangement of the N-hydrogen substituted compound to form the thermally stable 8-coordinate homoleptic β-ketoiminate (IV').…”
Section: Metal β-Ketoiminato Complexesmentioning
confidence: 99%