Divalent tin and lead complexes of a bulky salen ligand: the syntheses and structures of [SalenBut,Me]Sn and [SalenBut,Me]Pb

Kuchta, Matthew C.; Hahn, Juliet M.; Parkin, Gerard

doi:10.1039/a905490a

Cited by 24 publications

(13 citation statements)

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“…Thus, the presence of ligands with donor side arms on the germanium or the tin element can (by transfer of electron density) reduce the deficit on 37 is, to our knowledge, the first example of an intramolecular base stabilized homoleptic dialkylgermylene. Various amino-, phosphino-, thioalkoxy-, alkoxy-and aryloxy-divalent species have also been isolated in monomeric form owing to this method of stabilization; one should mention in particular the studies of Jutzi and co-workers, 28,32,54,71 Veith and coworkers, 15,18,40,66 Parkin and co-workers, 67 Jurkschat and co-workers, 77,78 Dias and co-workers 31,35,42,69,80,81 and Roesky and co-workers. …”

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Three‐coordinate divalent Group 14 element derivatives and related compounds

Saur

Alonso

Barrau

2005

Applied Organom Chemis

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INTRODUCTIONThis paper is an overview of a particular part of our systematic investigation of the divalent germanium and tin species focusing on the use in this chemistry of a β-diketiminato ligand with no encumbering aryl groups on the nitrogen. The bidentate three-atom bridging ligand L 2 (L 2 = PhNC(Me)CHC(Me)NPh), by its remarkable stabilizing properties, allows for easy isolation of subvalent germanium and tin compounds and, as such, permits a general insight on the chemistry of such species. The emphasis here will be on the divalent species L 2 (X)M (M = Ge, Sn), the germanechalcogenones L 2 (Cl)Ge Y, the transition- L (n−x) and the cationic ger- IntroductionThe divalent species of Group 14 elements are the heavier carbene analogues; for recent reviews, see Refs 6-10. They are generally transient species. As a general rule, when these species contain unfunctionalized organic ligands, they undergo rapid oligomerization and polymerization. In the last two decades, two principal methods of stabilization have been particularly investigated. Thus, various kinetically and/or thermodynamically stabilized divalent germanium and tin compounds have been isolated in a monomeric state. 1 -5,11 -81 The use of bulky groups bound to the Group 14 element to prevent aggregation permitted the first syntheses of stable monomer divalent species; the most noticeable are the dialkyl-germylene and -stannylene reported by Lappert and co-workers, 12 the first stable monomeric arylgermylene ((Mes * ) 2 Ge (Mes * = 2,4,6-t Bu 3 -phenyl)) described by Du Mont and co-workers, 14 and the well-known aryl-germylene and -stannylene Tbt(Tip)M 14 (M 14 = Ge, Sn; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Tip = 2,4,6-i Pr 3 -phenyl) of Okazaki and co-workers. 25,29The ligand backbone may also play an important role in improving stability. Thus, the presence of ligands with donor side arms on the germanium or the tin element can (by transfer of electron density) reduce the deficit on 37 is, to our knowledge, the first example of an intramolecular base stabilized homoleptic dialkylgermylene. Various amino-, phosphino-, thioalkoxy-, alkoxy-and aryloxy-divalent species have also been isolated in monomeric form owing to this method of stabilization; one should mention in particular the studies of Jutzi and co-workers, 28,32,54,71 Veith and coworkers, 15,18,40,66 Parkin and co-workers, 67 Jurkschat and co-workers, 77,78 Dias and co-workers 31,35,42,69,80,81 and Roesky and co-workers. Main Group Metal Compounds -5Although a large number of homoleptic divalent germanium and tin species have been isolated using these concepts of stabilization, there are fewer examples of heteroleptic compounds having been reported, though the first functional heteroleptic germylenes R(Cl)Ge (R = Et, Ph) were obtained as viscous oils in the 1970 by our group.6 Few solidstate structures of such heteroleptic compounds have been described. Noteworthy examples are in the area of thermodynamic stabilization, the acetylacetonatogermylene R(I)Ge (R = OC (Me) 46...

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Three‐coordinate divalent Group 14 element derivatives and related compounds

Saur

Alonso

Barrau

2005

Applied Organom Chemis

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“…The ligand bite angles (N1–M–O1) are gradually reduced in the sequence Ge > Sn > Pb (85.2, 80.9, 74.3°). The M–O1 bond lengths (1.88, 2.11, 2.44 Å) and M–N1 bond lengths (2.28, 2.43, 2.50 Å) increase as expected from the electronic features and are in good agreement with the interatomic distances reported for comparable germanium,20 tin,21,22 and lead21,23,24 complexes with N,O‐chelating ligands.…”

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confidence: 99%

Air‐Stable and Volatile Bis(pyridylalkenolato)germanium(II), ‐tin(II), and ‐lead(II) Complexes

Heidemann

Mathur

2013

Eur J Inorg Chem

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Keywords: Main group metals / Lead / Tin / Germanium / N,O ligands / Molecular precursor Homoleptic germanium(II), tin(II), and lead(II) complexes of the general formula M(2-PyCHCOCF 3 ) 2 (M = Ge, Sn, Pb; Py = pyridine) were synthesized by treating the corresponding silyl amides [M{N(SiMe 3 ) 2 } 2 ] with two equivalents of a 3,3,3trifluoro-1-(2-pyridyl)prop-1-en-2-ol (2-PyCHCOHCF 3 ) ligand. Single-crystal X-ray diffraction revealed the bidentate chelation of 2-PyCHCOHCF 3 , which imposes a distorted tri-[a] Chair

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“…9 In the literature several Schiff-base ligands have been reported and most recently, heptadentate (N 3 O 4 ) ones with various ring-substituted salicylaldehydes have been prepared and their coordination chemistry with a number of metal ions has been extensively investigated. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] Another class of N-functionalized aminephenol Schiff-base ligands such as 1,7-bis(2-hydroxybenzyl)-4-(p-aminobenzyl)diethylenetriamine (Bhabdt) 27 has been developed and used for the conjugation of proteins to label with radionuclides.…”

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“…J ¼ 14.0, 7.50);13 C NMR: a total of 23 peaks have been obtained at 38.57, 42.31, 48.81, 50.16, 50.46, 52.74, 57.76, 116.37, 116.51, 119.49, 119.58, 122.17, 122.28, 123.96, 128.50, 128.70, 129.12, 129.18, 129.94, 145.75, 146.85, 157.51, and 157.62; FAB-MS: Found: m/z 378 [M + H] + ; calcd. for C 23 -H 27 N 3 O 2 : 377; anal.…”

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confidence: 99%