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Adducts and cyclometallated derivatives of palladium(II) with some 1,4-benzodiazepin-2-ones: crystal and molecular structure of trans-dichlorobis[7-chloro-1-(cyclopropylmethyl)-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one] palladium(II)

Cinellu, Maria Agostina and Ganadu, Maria Luisa Margherita and Minghetti, Giovanni and Cariati, Francesco and Demartin, Francesco and Manassero, Mario (1988) Adducts and cyclometallated derivatives of palladium(II) with some 1,4-benzodiazepin-2-ones: crystal and molecular structure of trans-dichlorobis[7-chloro-1-(cyclopropylmethyl)-1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one] palladium(II). Inorganica Chimica Acta, Vol. 143 (2), p. 197-207. ISSN 0020-1693. Article.

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DOI: 10.1016/S0020-1693(00)83689-0

Abstract

The adducts trans-L2PdCl2 (1, L = Diazepam = 7- chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin -2-one; 5, L = Prazepam = 7-chloro-1-(cyclopropylmethyl)- 1,3-dihydro-5-phenyl-2H-1,4-benzodiazepin-2-one) were prepared by reaction of PdCl2 or (PhCN)2PdCl2 with Diazepam and Prazepam, respectively.
In the adducts, the benzodiazepines act as monodentate ligands through the 4-nitrogen atom, as shown by the structure of compound 5, determined by X-ray diffraction.
Two crystalline modifications have been characterized: 5a, trans-(Prazepam)2PdCl2/CHCl3 1/1, monoclinic, space group P21/n, a = 11.996(4), b = 13.678(5), c = 12.717(3) Å, β = 98.83(2), Z = 2, R = 0.032; 5b, trans-(Prazepam)2PdCl2/CH2Cl2 1/1, monoclinic, space group P21/c, a = 14.074(3), b = 14.622(7), c = 19.360(10) Å, β = 100.04(3), Z = 4, R = 0.076.
Cyclometallated derivatives [(L---H)PdCl]2, 2, L = Diazepam and 6, L = Prazepam, involving both C- and N-intramolecular coordination of the deprotonated ligands, have been obtained by reaction with Na2[PdCl4] in ethanol solution. In the dimeric species 2 and 6, the halide-bridge is easily split by reaction with Ph3P or Tl(acac), to give [(L---H)•(Ph3P)PdCl], (3, 7) and [(L---H)Pd(acac)] (4, 8) respectively.

Item Type:Article
ID Code:4895
Status:Published
Refereed:Yes
Uncontrolled Keywords:Palladium(II), cyclometallated derivatives, benzodiazepines
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Area 03 - Scienze chimiche > CHIM/12 Chimica dell'ambiente e dei beni culturali
Divisions:001 Università di Sassari > 01 Dipartimenti > Chimica
Publisher:Elsevier Science
ISSN:0020-1693
Deposited On:22 Nov 2010 10:31

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