A Square-Planar Complex of Platinum(0)

被引：21

作者：

Takeuchi, Katsuhiko ^{[1
,2
]}

Taguchi, Hiro-omi ^{[1
,2
]}

Tanigawa, Ippei ^{[1
,2
]}

Tsujimoto, Shota ^{[3
]}

Matsuo, Tsukasa ^{[3
]}

Tanaka, Hiromasa ^{[4
,5
]}

Yoshizawa, Kazunari ^{[4
,5
]}

Ozawa, Fumiyuki ^{[1
,2
]}

机构：

[1] Kyoto Univ, Int Res Ctr Elements Sci IRCELS, Inst Chem Res, Uji, Kyoto 6110011, Japan

[2] Kyoto Univ, IRCCS, Uji, Kyoto 6110011, Japan

[3] Kindai Univ, Fac Sci & Engn, Dept Appl Chem, Osaka 5778502, Japan

[4] Kyushu Univ, Inst Mat Chem & Engn, Int Res Ctr Mol Syst, Fukuoka 8190395, Japan

[5] Kyushu Univ, IRCCS, Fukuoka 8190395, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 49期

关键词：

phosphaalkene ligands; pincer complexes; platinum; relativistic effects; square-planar complexes; BULKY RIND GROUPS; DIANIONIC IRON; CHEMISTRY; PHOSPHAALKENE; LIGANDS; D(10);

D O I：

10.1002/anie.201609515

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The Pt-0 complex [Pt(PPh3)(Eind(2)-BPEP)] with a pyridine-based PNP-pincer-type phosphaalkene ligand (Eind(2)-BPEP) has a highly planar geometry around Pt with Sigma(Pt)=358.6 degrees. This coordination geometry is very uncommon for formal d(10) complexes, and the Pd and Ni homologues with the same ligands adopt distorted tetrahedral geometries. DFT calculations reveal that both the Pt and Pd complexes are M-0 species with nearly ten valence electrons on the metals whereas their atomic orbital occupancies are evidently different from one another. The Pt complex has a higher occupancy of the atomic 6s orbital because of strong s-d hybridization due to relativistic effects, thereby adopting a highly planar geometry reflecting the shape and orientation of the partially unoccupied dx2-y2 orbital.

引用

页码：15347 / 15350

页数：4

共 22 条

[1]

Albright TA, 2013, ORBITAL INTERACTIONS IN CHEMISTRY, 2ND EDITION, P1, DOI 10.1002/9781118558409

[2]

[Anonymous], ANGEW CHEM

[3] Dependence of relativistic effects on electronic configuration in the neutral atoms of d- and f-block elements [J].

Autschbach, J ;

Siekierski, S ;

Seth, M ;

Schwerdtfeger, P ;

Schwarz, WHE .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2002, 23 (08) :804-813

[4] Theoretical studies in palladium and platinum molecular chemistry [J].

Dedieu, A .

CHEMICAL REVIEWS, 2000, 100 (02) :543-600

[5]

Dugal-Tessier J., 2012, PHOSPHORUS 3 LIGANDS

[6] The nature of the bonding in transition-metal compounds [J].

Frenking, G ;

Fröhlich, N .

CHEMICAL REVIEWS, 2000, 100 (02) :717-774

[7] Phosphaalkene, phospholyl and phosphinine ligands: New tools in coordination chemistry and catalysis [J].

Le Floch, P .

COORDINATION CHEMISTRY REVIEWS, 2006, 250 (5-6) :627-681

[8] Synthesis and Characterization of Diphosphenes Bearing Fused-Ring Bulky Rind Groups [J].

Li, Baolin ;

Tsujimoto, Shota ;

Li, Yongming ;

Tsuji, Hayato ;

Tamao, Kohei ;

Hashizume, Daisuke ;

Matsuo, Tsukasa .

HETEROATOM CHEMISTRY, 2014, 25 (06) :612-618

[9] Fused-Ring Bulky "Rind" Groups Producing New Possibilities in Elemento-Organic Chemistry [J].

Matsuo, Tsukasa ;

Tamao, Kohei .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2015, 88 (09) :1201-1220

[10] Neutral and dianionic iron and ruthenium 1,4-diphosphabutadiene complexes [J].

Moores, A ;

Mézailles, N ;

Ricard, L ;

Mathey, F ;

Le Floch, P .

CHEMICAL COMMUNICATIONS, 2003, (15) :1914-1915

← 1 2 3 →