Crystal structure and sup 13 C and sup 195 Pt NMR spectra of an. alpha. -pyrrolidonate-bridged binuclear platinum(II) complex, (Pt sub 2 (NH sub 3 ) sub 4 (C sub 4 H sub 6 NO) sub 2 ) sub 2 (PF sub 6 ) sub 3 (NO sub 3 )ter dot H sub 2 O

Journal Article · Wed Jul 26 00:00:00 EDT 1989 · Inorganic Chemistry; (USA)

DOI:https://doi.org/10.1021/ic00314a017· OSTI ID:7108020

Matsumoto, Kazuko ^[1]; Miyamae, Hiroshi ^[2]; Moriyama, Hiroshi ^[3]

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1. Waseda Univ., Tokyo (Japan)
2. Josai Univ., Saitam (Japan)
3. National Chemical Lab. for Industry, Ibaraki (Japan)

The crystal structure and {sup 13}C and {sup 195}Pt NMR spectra of the amidate-bridged binuclear Pt(II) complex (Pt{sub 2}(NH{sub 3}){sub 4}(C{sub 4}H{sub 6}N-O){sub 2}){sub 2}(PF{sub 6}){sub 3}(NO{sub 3}){center dot}H{sub 2}O show that although the complex cation is binuclear in solution, it is tetranuclear in the solid state, where its structure is basically identical with that of the previously reported cis-diammineplatinum {alpha}-pyrrolidonate tan cation (Pt{sub 4}-(NH{sub 3}){sub 8}(C{sub 4}H{sub 6}NO){sub 4}){sup 6+}. The amidate-bridged Pt-Pt distance in the present complex is 3.033 (2) {angstrom}, and the central Pt-Pt distance, without the amidate bridge, is 3.186 (2) {angstrom}. These distances are significantly longer than the corresponding ones already reported for the {alpha}-pyridonate complexes (Pt{sub 2}(NH{sub 3}){sub 4}(C{sub 5}H{sub 4}NO){sub 2}){sub 2}{sup 4+} and (Pt{sub 2}(en){sub 2}(C{sub 5}H{sub 4}NO){sub 2}){sub 2}{sup 4+}. Both {sup 13}C and {sup 195}Pt NMR spectra of the present complex in D{sub 2}O revealed the existence of head-to-head (H-H) and head-to-tail (H-T) isomers, indicating that the H-H isomer very rapidly isomerizes to the H-T isomer on dissolution in water and both isomers exist in equilibrium in solution. This rapid isomerization contrasts to the case of the corresponding {alpha}-pyridonate complex (Pt{sub 2}(en){sub 2}(C{sub 5}H{sub 4}NO){sub 2}){sup 2+}, whose isomerization equilibrium requires about 2 days to be established. 24 refs., 5 figs., 4 tabs.

• OSTI ID: 7108020
• Journal Information: Inorganic Chemistry; (USA), Vol. 28:15; ISSN 0020-1669
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AMINES
CRYSTAL STRUCTURE
AROMATICS
ORGANIC FLUORINE COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PLATINUM COMPLEXES
CARBON 13
EXPERIMENTAL DATA
NMR SPECTRA
PLATINUM 195
CARBON ISOTOPES
COMPLEXES
DATA
DAYS LIVING RADIOISOTOPES
EVEN-ODD NUCLEI
HEAVY NUCLEI
INFORMATION
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PLATINUM ISOTOPES
RADIOISOTOPES
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation