Synthesis and reactivity of cationic pentacoordinate nitrosyl complexes

Ghedini, Mauro; Dolcetti, Giuliano; Gandolfi, Ottavio; Giovannitti, Bruno

doi:10.1021/ic50164a015

Cited by 15 publications

(3 citation statements)

References 9 publications

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“…Though the two limiting forms of the nitrosyl group cannot unequivocally be distinguished on the basis of v(NO) frequency, stretching frequencies in the 1840 cm" region can almost surely be assigned to a linear bonded nitrosyl group. Thus for the four-coordinate complexes 7,8,9,10,11, the most reasonable geometry around the metal is square planar with the metal in the d" configuration and the nitrosyl group linearly bonded as sketched in (I).…”

Section: Resultsmentioning

confidence: 99%

“…The mixture was stirred at room temperature for 12 h. The yellow precipitate was filtered and characterized as Ir(NO)(P(C.H,)3)3 (19). The brown solution was taken to dryness and 5 ml of THF (for 7) or diethylether (for 8,9,10,11) were added. The suspension was passed down a small silica gel column eluting with THF or diethylether.…”

Section: Solvents and Chemicalsmentioning

confidence: 99%

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ChemInform Abstract: IRIDIUM AND RHODIUM NITROSYL O‐CATECHOLATO METAL COMPLEXES

Ghedini¹,

Denti²,

Dolcetti³

1978

Chemischer Informationsdienst

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Abstract. The synthesisand characterization of several novel tetra and pentacoordinate catecholato metal nitrosyl complexes of the type Ir(NO)(1,2-02C.H3-3 or 4-R)-P(C.H,)3): 3-R = isoC 3H,; 4-R = COOH, H, CH 3, terC.H.; and M(NO)(1,2-02C.H3-4-R)(P(CoH,)3),: M = Ir and Rh; R = N0 2 , CHO, COOCH,; M = Rh; R = H; are reported together with their IR spectra. Two different classesof cathecolato complexes are obtained, tetracoordinate and pentacoordinate. The pentacoordinate complexes achieve tetracoordination, in solution, by spontaneous and reversible release of a phosphine molecule.The separation of the crystallinespecies seems to be determined either by the electron withdrawing or releasing power of the cathecolato ring substituents rather than by the solubility of the single species in our preparative conditions. The possibility for the pentacoordinate complexes to have a packed trigonal bipyramidgeometry with axial bent nitrosyl NO-and axial equatorial catechol ligand is supported by the easy phosphine dissociation to form the tetracoordinate, which has been observed both in solution and in field desorption mass spectra measurements. For the tetracoordinate complexes a square planar geometry with linear nitrosyl, NO+, is proposed.

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Section: Resultsmentioning

confidence: 99%

Section: Solvents and Chemicalsmentioning

confidence: 99%

ChemInform Abstract: IRIDIUM AND RHODIUM NITROSYL O‐CATECHOLATO METAL COMPLEXES

Ghedini¹,

Denti²,

Dolcetti³

1978

Chemischer Informationsdienst

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show abstract

“…Table 5. Fractional atomic co-ordinates ( x lo4) with estimated standard deviations in parentheses for the non-hydrogen atoms Xlu 0 -1 443 (5) 1 396(4) 4 359(5) -4 738(13) -I 184 (13) -2 574 ( 12) -426 ( 14) 886 ( 15) 975( 14) 881(13) -980 (20) -992 ( 13) 143( 20) 1683 (19) 1 678( 18) 2 458 (23) 2 394 (21) 1617 (19) 921 (18) 29( 19) 920( 24 Data collection and processing. Siemens AED diffractometer, 8-28 scan mode, using niobium-filtered Mo-K, radiation; all the reflections with 8 in the range 3-24" were measured.…”

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confidence: 99%