Stereochemistry of Transition-Metal Dinitrosyl Complexes. A Molecular Orbital Rationale for the Attracto and Repulso Conformations

被引:4
作者
Ghosh, Abhik [1 ]
Conradie, Jeanet [1 ,2 ]
机构
[1] Univ Tromso, Dept Chem, N-9037 Tromso, Norway
[2] Univ Free State, Dept Chem, ZA-9300 Bloemfontein, South Africa
基金
新加坡国家研究基金会;
关键词
RAY CRYSTAL-STRUCTURES; IRON-SULFUR CLUSTERS; ELECTRONIC-STRUCTURE; ROUSSINS RED; NITRIC-OXIDE; NO; REACTIVITY; CHEMISTRY; STRAIGHT; LIGANDS;
D O I
10.1021/acs.inorgchem.9b00266
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Transition-metal dinitrosyl complexes constitute a fairly large class of compounds, exemplified by some 500 structures in the Cambridge Structural Database. While many of the complexes exhibit a claw-like cis-attracto conformation, a handful of them exhibit a peculiar repulso conformation, in which the two NO groups are splayed outward and away from each other. Surprisingly, no computational study to date has attempted to explain the existence of these two limiting conformations of cis-dinitrosyl complexes. Careful examination of the large body of structural data and density-functional-theory-based molecular orbital analyses has identified both specific Enemark-Feltham electron counts and metal-ligand orbital interactions as crucial to each of the two conformations. Thus, the common attracto conformation, which is favored by as many as four metal(d)-NO(pi*) orbital interactions, is observed most characteristically in four- and five-coordinate cis-{M(NO)(2)}(8) complexes. The rarer repulso conformation, characterized by an unusually wide NMN' angle, appears to be typical of pseudotetrahedral {M(NO )(2)}(10) complexes involving 4d and 5d transition metals. These complexes exhibit an a(1)-symmetry (under a C (2v) molecular point group) metal(d)-NO(pi*) orbital interaction that uniquely favors a repulso geometry. This orbital interaction, however, appears to be weaker for 3d orbitals, which are significantly smaller than 4d and 5d orbitals. Pseudotetrahedral {M(NO )(2)}(10)complexes involving a 3d transition metal accordingly thus tend to exhibit an attracto conformation for hard, nitrogen-based supporting ligands but repulso-like/borderline conformations for soft phosphine- and thioether-type supporting ligands.
引用
收藏
页码:5943 / 5948
页数:6
相关论文
共 67 条
[1]   STEREOCHEMISTRY OF TETRAHEDRAL COMPLEXES OF GROUP VIII METALS - CRYSTAL AND MOLECULAR-STRUCTURES OF DINITROSYLCARBONYLTRIPHENYLPHOSPHINEIRON, FE(NO)2(CO)(PPH3), AND OF DINITROSYLBIS(TRIPHENYLPHOSPHINE(IRON, FE(NO)2(PPH3)2 [J].
ALBANO, VG ;
ARANEO, A ;
BELLON, PL ;
CIANI, G ;
MANASSER.M .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1974, 67 (03) :413-422
[2]   A new fundamental type of conformational isomerism [J].
Canfield, Peter J. ;
Blake, Iain M. ;
Cai, Zheng-Li ;
Luck, Ian J. ;
Krausz, Elmars ;
Kobayashi, Rika ;
Reimers, Jeffrey R. ;
Crossley, Maxwell J. .
NATURE CHEMISTRY, 2018, 10 (06) :615-624
[3]   Molecular structure and conformation of dinitrosylheme [J].
Conradie, J ;
Wondimagegn, T ;
Ghosh, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (17) :4968-4969
[4]   Electronic structure and FeNO conformation of nonheme Iron-Thiolate-NO complexes: An experimental and DFT study [J].
Conradie, Jeanet ;
Quarless, Duncan A., Jr. ;
Hsu, Hua-Fen ;
Harrop, Todd C. ;
Lippard, Stephen J. ;
Koch, Stephen A. ;
Ghosh, Abhik .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (34) :10446-10456
[5]   DFT calculations on the spin-crossover complex Fe(salen)(NO): a quest for the best functional [J].
Conradie, Jeanet ;
Ghosh, Abhik .
JOURNAL OF PHYSICAL CHEMISTRY B, 2007, 111 (44) :12621-12624
[6]   Electronic structure of trigonal-planar transition-metal-imido complexes: Spin-state energetics, spin-density profiles, and the remarkable performance of the OLYP functional [J].
Conradie, Jeanet ;
Ghosh, Abhik .
JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2007, 3 (03) :689-702
[7]   Stereochemical Diversity of {MNO}10 Complexes: Molecular Orbital Analyses of Nickel and Copper Nitrosyls [J].
Conradie, Jeanet ;
Ghosh, Abhik .
INORGANIC CHEMISTRY, 2014, 53 (10) :4847-4855
[8]   Correlation between the FeNO Angle and d-p Mixing in {FeNO}7 Complexes [J].
Conradie, Jeanet ;
Ghosh, Abhik .
INORGANIC CHEMISTRY, 2011, 50 (10) :4223-4225
[9]   Understanding the Unusually Straight: A Search For MO Insights into Linear {FeNO}7 Units [J].
Conradie, Jeanet ;
Hopmann, Kathrin H. ;
Ghosh, Abhik .
JOURNAL OF PHYSICAL CHEMISTRY B, 2010, 114 (25) :8517-8524
[10]   When being straight bends rules:: A rationale for the linear FeNO unit in the low-spin square-pyramidal {FeNO}7 tetracyanonitrosylferrate(2-) anion [J].
Conradie, Jeanet ;
Ghosh, Abhik .
JOURNAL OF INORGANIC BIOCHEMISTRY, 2006, 100 (12) :2069-2073