Reactions of a Platinum(II) Agostic Complex: Decyclometalation, Dicyclometalation, and Solvent-Switchable Formation of a Rollover Complex

被引：47

作者：

Crosby, Sarah H. ^{[1
]}

Clarkson, Guy J. ^{[1
]}

Rourke, Jonathan P. ^{[1
]}

机构：

[1] Univ Warwick, Dept Chem, Coventry CV4 7AL, W Midlands, England

来源：

ORGANOMETALLICS | 2011年 / 30卷 / 13期

关键词：

C-H ACTIVATION; BOND ACTIVATION; MOLECULAR-STRUCTURE; CRYSTAL-STRUCTURE; GAS-PHASE; DERIVATIVES; DINUCLEAR; CYCLOMETALATION; TRANSPHOBIA;

D O I：

10.1021/om200293e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Good donor ligands react with an sp(2) cyclometalated complex of platinum containing an agostic interaction, initially causing displacement of the agostic interaction and decyclometalation. Eventually, these complexes rearrange to give sterically less congested complexes containing an sp(3) cydometalated group. The same end products are observed even with poor donor ligands that do not displace the agostic interaction, and this, together with other results, suggests to us that the route to the end products goes via a different agostic species. These sp(3) cyclometalated complexes can be made to dicyclometalate via the simple expedient of adding water/base. Finally, dissolution of the agostic complex in DMSO results in a reversible "rollover" reaction, giving a C(Lambda)C chelated ligand.

引用

页码：3603 / 3609

页数：7

共 43 条

[31] Perdew JP, 1997, PHYS REV LETT, V78, P1396, DOI 10.1103/PhysRevLett.77.3865
[32] The σ-CAM mechanism:: σ complexes as the basis of σ-bond metathesis at late-transition-metal centers
Perutz, Robin N.
Sabo-Etienne, Sylviane
[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (15) : 2578 - 2592
[33] Platinum(II) N-heterocyclic carbene complexes: coordination and cyclometallation
Petretto, Giacomo L.
Wang, Miao
Zucca, Antonio
Rourke, Jonathan P.
[J]. DALTON TRANSACTIONS, 2010, 39 (33) : 7822 - 7825
[34] Bifunctional pincer-type organometallics as substrates for organic transformations and as novel building blocks for polymetallic materials
Rodríguez, G
Albrecht, M
Schoenmaker, J
Ford, A
Lutz, M
Spek, AL
van Koten, G
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (18) : 5127 - 5138
[35] SYNTHESIS AND PROPERTIES OF (+-)-TRANS-(ETA-2-ALKENE)(4-ALKYLOXY-4'-STILBAZOLE)DICHLOROPLATINUM - A REMARKABLE FAMILY OF LOW-MELTING METALLOMESOGENS
ROURKE, JP
FANIZZI, FP
BRUCE, DW
DUNMUR, DA
MAITLIS, PM
[J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1992, (20): : 3009 - 3014
[36] Sheldrick G. M., 1997, SHELXL-97, Programs for Crystal Structure Analysis
[37] ROLL-OVER 3-METALLATION OF COORDINATED 2,2'-BIPYRIDYL IN THE THERMAL REARRANGEMENT OF DIARYL(BIPYRIDYL)PLATINUM(II) COMPLEXES - MOLECULAR-STRUCTURE OF (MU-BIDYL)[PTPH(BUTPY)]2
SKAPSKI, AC
SUTCLIFFE, VF
YOUNG, GB
[J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1985, (09) : 609 - 611
[38] TeVelde G., 1992, J COMP PHYSIOL, V99, P84, DOI DOI 10.1016/0021-9991(92)90277-6
[39] Mono- and di-nuclear complexes of ortho-palladated and -platinated 4,4′-dimethylazobenzene with bis(diphenylphosphino)methane.: More data on transphobia
Vicente, J
Arcas, A
Bautista, D
de Arellano, MCR
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2002, 663 (1-2) : 164 - 172
[40] Dinuclear C,N,C cyclometalated platinum derivatives with bridging delocalized ligands.: Fourfold deprotonation of 6,6′-diphenyl-2,2′-bipyridine, H4L, promoted by "Pt(R)2" fragments (R = Me, Ph).: Crystal structures of [Pt2(L)(3,5-Me2py)2] and {Pt2(L)(dppe)}2 (dppe=1,2-bis(diphenylphosphino)ethane).: X-ray powder diffraction of [Pt2(L)(CO)2]
Zucca, A
Petretto, GL
Stoccoro, S
Cinellu, MA
Minghetti, G
Manassero, M
Manassero, C
Male, L
Albinati, A
[J]. ORGANOMETALLICS, 2006, 25 (09) : 2253 - 2265

← 1 2 3 4 5 →