2001
DOI: 10.1002/1521-3749(200105)627:5<935::aid-zaac935>3.0.co;2-j
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Mononitrosyl- undtrans-Dinitrosyl-Komplexe von Phthalocyaninaten des Mangans und Rheniums

Abstract: Professor Kurt Dehnicke zum 70. Geburtstag gewidmet Inhaltsu È bersicht. Tetra(n-butyl)ammonium-oder Di(triphenylphosphan)iminium nitrosylacidophthalocyaninato(2±)manganat, (cat)[Mn(NO)(X)pc 2± ] (X = ONO, NCO, N 3 ; cat = n Bu 4 N, PNP) wird aus [Mn(X)pc 2± ], (cat)NO 2 und ( n Bu 4 N)BH 4 in CH 2 Cl 2 oder aus Nitrosylphthalocyaninato(2±)mangan, [Mn(NO)pc 2± ] und ( n Bu 4 N)X (X = ONO, NCO, N 3 , NCS) bei T < 120°C dargestellt. [Mn(NO)pc 2± ] fa È llt aus einer Lo È sung von [Mn(NO)(X)pc 2± ] ± in Methanol … Show more

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Cited by 21 publications
(17 citation statements)
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“…This interaction also results in deviation of the structure from idealized octahedral geometry to give a noticeable decrease in the O–Re–N angles, which range from 76.41 to 80.38 degrees. The distortions of this type were also observed in closely analogous complexes containing aromatic di‐ and tetra‐imines in cis position with respect to Re–O(–P) bond,, in the latter case the whole tetradentate phthalocyaninato aromatic system being bent to shorten the distance to the oxygen atom of a rather bulky phosphine oxide ligand. These observations indicate the presence of an interaction between the phosphine oxide ligand and the diimine aromatic system that can be assigned to a combination of electrostatic attraction between negatively charged PO oxygen atom and positively charged diimine carbon atoms (see Table S2) together with a possible donor–acceptor interaction of the oxygen loan pair and unoccupied π*‐orbitals of the diimine aromatic system, which stabilize relatively weak bonding of the hard donor ligand to the soft metal center.…”
Section: Resultsmentioning
confidence: 99%
“…This interaction also results in deviation of the structure from idealized octahedral geometry to give a noticeable decrease in the O–Re–N angles, which range from 76.41 to 80.38 degrees. The distortions of this type were also observed in closely analogous complexes containing aromatic di‐ and tetra‐imines in cis position with respect to Re–O(–P) bond,, in the latter case the whole tetradentate phthalocyaninato aromatic system being bent to shorten the distance to the oxygen atom of a rather bulky phosphine oxide ligand. These observations indicate the presence of an interaction between the phosphine oxide ligand and the diimine aromatic system that can be assigned to a combination of electrostatic attraction between negatively charged PO oxygen atom and positively charged diimine carbon atoms (see Table S2) together with a possible donor–acceptor interaction of the oxygen loan pair and unoccupied π*‐orbitals of the diimine aromatic system, which stabilize relatively weak bonding of the hard donor ligand to the soft metal center.…”
Section: Resultsmentioning
confidence: 99%
“…The trans arrangement of the two bulky triphenylphosphine molecules causes the cis location of the nitrosyl groups with respect to PPh 3 (-acid ligands). This is due to the electronic influence of the [41]. In all the other structurally characterised mononuclear dinitrosyl rhenium complexes NO ligands adopt a bent structure [42][43][44][45].…”
Section: Computational Detailsmentioning
confidence: 99%
“…However, a number of complexes do not fit this paradigm and feature linear MNO angles, even though n > 6, posing a theoretical challenge. Thus, using density functional theory (DFT, PW91/TZP), we have attempted to understand the relative linearity of the MNO units in a unique trans-{Mn(NO) 2 } 8 complex (see [10,11] for our earlier studies in this area), the Mn(Pc)(NO) 2 ] À (Pc = phthalocyaninato) anion [12]. (All geometry optimizations were carried out using the ADF program system, the VWN ''local'' functional, Perdew-Wang 1991 (PW91) gradient-corrected functionals for both exchange and correlation, Slater-type triple-f plus polarization (TZP) basis sets, and a fine mesh for numerical integration of matrix elements.…”
mentioning
confidence: 99%
“…These orbital interactions would not be symmetry-allowed if the axial ligands were present in an upright or transoid orientation. In contrast to the trans{Fe(NO) 2 } 8 porphyrin species, the X-ray crystal structure of an [Mn(Pc)(NO) 2 ] À salt reveals a near-D 4h anion, with a near-linear ON-Mn-NO arrangement [12]. What accounts for the linearity of the {Mn(NO) 2 } 8 group?…”
mentioning
confidence: 99%
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