New water-soluble azido- and derived tetrazolato-platinum(II) complexes with PTA. Easy metal-mediated synthesis and isolation of 5-substituted tetrazoles.
The water-soluble four- and five-coordinate diazido-platinum(II) complexes cis-[Pt(N3)2(PTA)2] (1) (PTA = 1,3,5-triaza-7-phosphaadamantane), cis-[Pt(N3)2(Me-PTA)2]I2 (2) (Me-PTA = N-methyl-1,3,5-triaza-7-phosphaadamantane cation) and [Pt(N3)2(PTA)3] (3) were obtained by reactions of cis-[Pt(N3)2(PPh3)2] with PTA or [Me-PTA]I in dichloromethane. [2 + 3] cycloadditions of with organonitriles NCR gave the bis(tetrazolato) complexes trans-[Pt(N4CR)2(PTA)2] (R = Ph (4), 4-ClC6H4 (5) or 3-NC5H4 (6)), the reactions being greatly accelerated by microwave irradiation. 5-R-1H-Tetrazoles N4CR (R = Ph, 4-ClC6H4 and 3-NC5H4) were easily liberated from the tetrazolato complexes and isolated in high yields, in a single-pot process, upon reaction with aqueous diluted HCl, with concomitant formation of the water soluble cis-[Pt(Cl)2(PTA-H)2] complex 7. Alternatively, in a less convenient method, the tetrazoles could be liberated on reaction of 4-6 with propionitrile which also leads to the dicyano trans-[Pt(CN)2(PTA)2] complex 8. The compounds were characterized by IR, 1H, 13C and 31P[1H] NMR spectroscopies, FAB+-MS or ESI-MS, elemental analyses and (for and 4) also by X-ray diffraction.
Smoleński
Piotr
P
Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal.
Mukhopadhyay
Suman
S
Guedes da Silva
M Fátima C
MF
Charmier
M Adília Januário
MA
Pombeiro
Armando J L
AJ
D000218:Adamantane / Q000031:analogs & derivatives* / Q000737:chemistry; D001386:Azides / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008872:Microwaves; D009942:Organometallic Compounds / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D012995:Solubility; D013055:Spectrophotometry, Infrared; D013777:Tetrazoles / Q000138:chemical synthesis* / Q000302:isolation & purification*; D014867:Water / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
C501763:1,3,5-triaza-7-phosphaadamantane; D001386:Azides; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D013777:Tetrazoles; D014867:Water; D015032:Zinc; D000218:Adamantane