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Synthesis of asymmetric Rh/sub 2//sup 4+/ complexes. X-ray crystal structure of Rh/sub 2/(form)/sub 3/(NO/sub 3/)(PPh/sub 3/)/center dot/0. 5CH/sub 2/Cl/sub 2/ and Rh/sub 2/(form)/sub 3/(NO/sub 3/)(C/sub 5/H/sub 5/N) (form = N,N'-di-p-tolylformamidinate)

Journal Article · · Inorg. Chem.; (United States)
DOI:https://doi.org/10.1021/ic00300a031· OSTI ID:5761824
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The reaction of the paramagnetic Rh/sub 2//sup 5+/ complex Rh/sub 2/(form)/sub 3/(NO/sub 3/)/sub 2/ (form = N,N'-di-p-tolylformamidinate) with an excess of the neutral ligands PPh/sub 3/, pyridine, and dimethylamine leads, via reductive elimination of one nitrate group, to the formation of the asymmetric Rh/sub 2//sup 4+/ complexes Rh/sub 2/(form)/sub 3/(NO/sub 3/)L L = PPh/sub 3/ (1), pyridine (2), N(CH/sub 3/)/sub 2/H (3). The two rhodium atoms in complexes 1-3 display different coordinations and reduced average formal oxidation states. The complexes have been characterized by IR, /sup 31/P NMR, and /sup 103/Rh NMR spectroscopic methods, which point out the nonequivalence of the two rhodium atoms. Complexes 1 and 2 have also been characterized by single-crystal X-ray analysis. Complex 1 belongs to the monoclinic space group system P2/sub 1//n, with a = 21.529 (3) /angstrom/; b = 23.990 (3) /angstrom/, c = 11.944 (1) /angstrom/, /beta/ = 102.13 (4)/degree/, Z = 4, and R = 0.057 for 2046 reflections with I > 3/sigma/(I). The crystal structure reveals that one of the three formamidinate groups spanning the dimetal center (Rh-Rh = 2.498 (2) /angstrom/) is bonded in an unusual way, namely, /sigma/,/sigma/-N,N' with a localized double bond. Complex 2 forms monoclinic crystals in space group P2/sub 1//c with a = 10.238 (1) /angstrom/, b = 16.567 (2) /angstrom/, /beta/ = 955.6 (3)/degree/, Z = 4, and R = 0.041 for 3392 reflections with I > 3/sigma/(I). In complexes 2 and 3 of all the bridging ligands are bonded in the usual fashion, namely, /sigma/,/sigma/-N,N' with delocalized double bonds. 18 refs., 3 figs., 6 tabs..
Research Organization:
Universite di Messina (Italy)
OSTI ID:
5761824
Journal Information:
Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 28:1; ISSN INOCA
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
AROMATICS
COMPLEXES
CRYSTAL STRUCTURE
DATA
EXPERIMENTAL DATA
INFORMATION
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
MINUTES LIVING RADIOISOTOPES
NITRATES
NITROGEN COMPOUNDS
NMR SPECTRA
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
OXYGEN COMPOUNDS
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
RADIOISOTOPES
RHODIUM 103
RHODIUM COMPLEXES
RHODIUM ISOTOPES
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES