Dinuclear palladium(ii) complexes with bridging amidate ligands.
New homonuclear dimeric Pd(ii) complexes have been synthesized by the reaction of Pd(en)(2+) or Pd(bipy)(2+) (where en = ethylenediamine and bipy = 2,2'-bipyridine) units with acetamide or by the Pd(ii) mediated hydrolysis of CH(3)CN. In these dimers the two metal centers are bridged by either two amidates or by the combination of one hydroxo group and one amidate ligand. The crystal structures of complexes {[Pd(bipy)](2)(micro-1,3-CH(3)CONH)(2)}(NO(3))(2).H(2)O.1/2(CH(3))(2)CO.1/2CH(3)CN () and {[Pd(bipy)](2)(micro-1,3-CH(3)CONH)(2)}(OTf)(2) () showed intrametallic Pd-Pd distances of 2.8480(8) A () and 2.8384(7) A (), respectively, in accordance with the accepted values for a strong Pd-Pd interaction. The presence of pi[dot dot dot]pi interactions between the bipyridine ligands on the di-micro-amidate complexes of Pd(bipy)(2+) shortens the distance between the two Pd centers and allows the formation of the metal-metal interaction. By contrast, the crystal structure of complex {[Pd(en)](2)(micro-1,3-CH(3)CONH)(2)}(OTf)(2).H(2)O (), (where OTf = triflate) where there is no pi[dot dot dot]pi interaction between the ligands on the metal centers, is also reported, and no Pd-Pd interaction is observed. Additionally, one of the complexes, {[Pd(en)](2)(micro-OH)(micro-CH(3)CONH)}(NO(3))(2) (), presents an interesting hydrogen bonded 3-D network formed by nitrate ions and water molecules. All complexes have been characterized by infrared and (1)H NMR spectroscopy.
Adrian
Rafael A
RA
Department of Chemistry, The University of Texas at San Antonio, San Antonio, TX 78249-0698, USA.
Zhu
Shourong
S
Powell
Douglas R
DR
Broker
Grant A
GA
Tiekink
Edward R T
ER
Walmsley
Judith A
JA
D000577:Amides / Q000737:chemistry*; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D005029:Ethylenediamines / Q000737:chemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010165:Palladium / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry
D000577:Amides; D001952:Bridged-Ring Compounds; D005029:Ethylenediamines; D008024:Ligands; D009942:Organometallic Compounds; D011725:Pyridines; D010165:Palladium; C031234:ethylenediamine