2013
DOI: 10.1002/ejic.201300808
|View full text |Cite
|
Sign up to set email alerts
|

Donor Behaviour of Anionic and Asymmetric Phosphanido Derivatives of Platinum and Palladium

Abstract: Keywords: Metal-metal interactions / P ligands / Palladium / Platinum / Structure elucidationThe reactions of [Ag(OClO 3 )(PPh 3 )] F 5 )(tht)] (M = Pt, Pd; hq = 8-hydroxyquinolinate, bq = benzoquinolinate, pic = picolinate, tht = tetrahydrothiophene) afford the corresponding neutral adducts [(C 6 F 5 ) 2 Pt-(μ-PPh 2 ) 2 (μ-AgPPh 3 )M(bq)] (M = Pt, 1; Pd, 2), [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 (μ-AgPPh 3 )M(hq)] (M = Pt, 3; Pd, 4) [(C 6 F 5 ) 2 Pt(μ-PPh 2 ) 2 -(μ-AgPPh 3 )Pt(C 6 F 5 )(tht)] (5) and [(C 6 F 5 ) 2 Pt(… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
2
1
1

Citation Types

0
9
0

Year Published

2014
2014
2018
2018

Publication Types

Select...
8

Relationship

2
6

Authors

Journals

citations
Cited by 12 publications
(9 citation statements)
references
References 69 publications
0
9
0
Order By: Relevance
“…The 31 P NMR spectrum in acetone-d 6 showed signals in the region from 125 to 130 ppm ascribable to the bridging diphenylphosphinito P 1 , around 14 ppm for the bridging diphenylphosphanide P 2 and at δ −142 and δ −152 for the bridging diphenylphosphanides P 4 and P 3 respectively. Although it was impossible to assign each resonance to the specific corresponding solvento species, it was ascertained by 1 H EXSY and 31 P{ 1 H} EXSY that the complexes contained H 2 O, CH 3 CN and acetone as labile ligands bonded to Pt 3 , and that all these solvento species were in equilibrium. In fact, exchange cross peaks between signals at δ 2.84 (free H 2 O in acetone) and δ 3.37 (coordinated H 2 O), as well as between overlapped signals at δ 2.1 (free acetone but also acetonitrile in acetone) and δ from 2.3 to 2.4 (coordinated acetone and coordinated acetonitrile) were present in the 1 H EXSY spectrum of an acetone-d 6 solution of 1-(solv)(solv′) at 298 K. Moreover, the 31 P{ 1 H} EXSY spectrum of the same solution showed at 298 K, in the phosphinite region, cross peaks between an intense peak at δ 126.9 and weak peaks at: δ 124.8, δ 128.8 and δ 129.5.…”
Section: Resultsmentioning
confidence: 99%
“…The 31 P NMR spectrum in acetone-d 6 showed signals in the region from 125 to 130 ppm ascribable to the bridging diphenylphosphinito P 1 , around 14 ppm for the bridging diphenylphosphanide P 2 and at δ −142 and δ −152 for the bridging diphenylphosphanides P 4 and P 3 respectively. Although it was impossible to assign each resonance to the specific corresponding solvento species, it was ascertained by 1 H EXSY and 31 P{ 1 H} EXSY that the complexes contained H 2 O, CH 3 CN and acetone as labile ligands bonded to Pt 3 , and that all these solvento species were in equilibrium. In fact, exchange cross peaks between signals at δ 2.84 (free H 2 O in acetone) and δ 3.37 (coordinated H 2 O), as well as between overlapped signals at δ 2.1 (free acetone but also acetonitrile in acetone) and δ from 2.3 to 2.4 (coordinated acetone and coordinated acetonitrile) were present in the 1 H EXSY spectrum of an acetone-d 6 solution of 1-(solv)(solv′) at 298 K. Moreover, the 31 P{ 1 H} EXSY spectrum of the same solution showed at 298 K, in the phosphinite region, cross peaks between an intense peak at δ 126.9 and weak peaks at: δ 124.8, δ 128.8 and δ 129.5.…”
Section: Resultsmentioning
confidence: 99%
“…Platinum diorganophosphanido complexes have been the object of intense study in the last years due to the rich chemistry they exhibit. NMR spectroscopy is a powerful technique for investigating the structure and dynamics in solution of such complexes, owing to the presence of several different spin 1/2 nuclei in these molecules ( 1 H, 31 P, 195 Pt, 13 C, and in several cases 19 F). Although NMR studies on this kind of complexes have been performed for several decades, some issues about 195 Pt NMR and 31 P NMR remain unclear.…”
Section: Introductionmentioning
confidence: 99%
“…Examples of structurally characterized heterobimetallic complexes with an unsupported d 8 –d 10 bond to Pd­(II) remain, however, very rare. Only a few examples have been reported, with Ag­(I), Au­(I), Tl­(I), Hg­(II), and, very recently by our group, with Cu­(I) . For the latter study of the structure and gas-phase thermochemistry of a Pd–Cu complex, cis -bis­(1,10-benzo­[ h ]­quinolinato)-palladium, 1 , [(bhq) 2 Pd­(II)] was chosen because it is structurally and electronically similar to proposed intermediates in Pd-catalyzed cross coupling reactions but more stable than other L 2 Pd II R 2 (R = alkyl, alkenyl, alkynyl) complexes, the reductive elimination being sterically blocked in the bis-chelate.…”
mentioning
confidence: 99%