Unique Fluxional Behavior. Synthesis, Structure, and Properties of Novel (Diamine)platinum(II) Complexes of 9-Fluorenylidene- and Benzhydrylidenemalonate Ligands
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- 作者：Young-A Lee ; Ok-Sang Jung ; Seong-Joo Kang ; Kang-Bong Lee ; and Youn Soo Sohn
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：March 13, 1996
- 年：1996
- 卷：35
- 期：6
- 页码：1641 - 1646
- 全文大小：175K
- 年卷期：v.35,no.6(March 13, 1996)
- ISSN：1520-510X
文摘
New (diamine)platinum(II) complexesA2PtX2 (A2 =trans-(±)-1,2-diaminocyclohexane (DACH),tetrahydro-4H-pyran-4,4-diylbis(methylamine)(THPDMA);X2 = 9-fluorenylidenemalonate(FM),benzhydrylidenemalonate(BHM)) have been synthesized and characterized by means of multinuclearNMR spectroscopy and X-ray analysis.(DACH)Pt(FM) crystallizes in space groupP21/c with eight formula units in acell of dimensions a = 20.071(7)Å, b = 12.717(3) Å, c = 24.512(6)Å, 
= 103.25(2)
, and V = 6090(3)Å.3 (DACH)Pt(BHM) crystallizesinspace group P
with four molecular units in a cell ofdimensions a = 11.048(3) Å, b =13.639(3) Å, c =14.043(6) Å, 
= 90.17(3), = 91.31(4),
= 89.98(3), and V = 2116(1)Å3. The platinum atom in bothcomplexes adopts a typical square planar arrangement with two nitrogenatoms in cis position. The9-fluorenylideneand benzhydrylidene groups of the amine ligands chelated to platinumare strikingly bent up by 88.8(3) and80.8(2), respectively, from the platinum square plane in thesolid state. Variable temperature 1H NMRspectraof the title complexes in dimethyl sulfoxide solution reveals that theamine proton resonances are sensitive to thefluxional motion of the remote arylidene groups, and suggests thatinterconversion occurs between two "bent-up"and "bent-down" forms. The prominent difference between the FMand BHM complexes is observed in solution,due to the presence or absence of the angle constraint of the anioniccoligands.
= 103.25(2), and V = 6090(3)Å.3 (DACH)Pt(BHM) crystallizesinspace group P with four molecular units in a cell ofdimensions a = 11.048(3) Å, b =13.639(3) Å, c =14.043(6) Å, = 90.17(3), = 91.31(4), = 89.98(3), and V = 2116(1)Å3. The platinum atom in bothcomplexes adopts a typical square planar arrangement with two nitrogenatoms in cis position. The9-fluorenylideneand benzhydrylidene groups of the amine ligands chelated to platinumare strikingly bent up by 88.8(3) and80.8(2), respectively, from the platinum square plane in thesolid state. Variable temperature 1H NMRspectraof the title complexes in dimethyl sulfoxide solution reveals that theamine proton resonances are sensitive to thefluxional motion of the remote arylidene groups, and suggests thatinterconversion occurs between two "bent-up"and "bent-down" forms. The prominent difference between the FMand BHM complexes is observed in solution,due to the presence or absence of the angle constraint of the anioniccoligands.