Synthesis of ylideplatinum(II) complexes via α-functionalised alkylplatinum(II) intermediates and some comparative data on palladium(II) complexes; X-ray structure of trans-[Pt(CH2PEt3)I(PEt3)2]I
“…Similar distances and angles were found in the structure of the cation ( 3 ) + (Figure ); the Pd−C(1)−S angle, at 111.3(5)°, is slightly opened, as often found in metal sulfur 7c-f,8,15c and phosphorus 20c,d,h,24 ylide complexes, and is assigned to steric repulsion factors. 7f,20d 3 Perspective view of the molecular structure of the cation ( 3 ) + . Thermal ellipsoids are at 50% probability.…”
Section: Resultssupporting
confidence: 73%
“…This seems to be a general trend in the reactivity of neutral nucleophiles with halo−halomethyl metal complexes. Many of these react, for example, with tertiary phosphines and give the fragments [X−M−CH 2 −PR 3 ] + X - ; moreover, the palladium complex (Me 2 S) 2 PdCl(CH 2 Cl) slowly decomposes in the air to a complex mixture also containing (Me 2 S)Pd(CH 2 SMe 2 )Cl 2 9a…”
Section: Resultsmentioning
confidence: 99%
“…However, the reverse reactivity has been observed at least once, i.e. , in the reaction of mer,cis- [(Me 3 P) 3 RhCl 2 (CH 2 Cl)] with an excess of PMe 3 , which displaces Cl - from Rh rather than RhCH 2 Cl, yielding trans -[(Me 3 P) 4 RhCl(CH 2 Cl)]Cl 20f…”
By reacting
trans-[PdCl(CH2Cl)(PBut
2H)2]
with tetrahydrothiophene (THT) or diethyl
sulfide in the presence of AgCF3SO3 or
TlPF6, the cationic palladium sulfur ylides
trans-[PdCl(CH2SR2)(PBut
2H)2]X
((2)CF3SO3 SR2 =
THT, X = CF3SO3;
(2)PF6 SR2 = THT, X
=
PF6; (3)PF6 SR2 =
SEt2, X = PF6) were isolated and
characterized. The crystal and molecular
structures of (2)CF3SO3
and (3)PF6 were solved by X-ray analyses.
The related complex
cis-[PdCl{CH2S(H)CH3}(PBut
2H)2]CF3SO3
was prepared by an independent route, i.e., by
the oxidative addition of the C−Cl bond of
Cl−CH2SCH3 to
Pd(PBut
2H)3 to form
trans-[PdCl(CH2SCH3)(PBut
2H)2],
which was then protonated with triflic acid.
“…Similar distances and angles were found in the structure of the cation ( 3 ) + (Figure ); the Pd−C(1)−S angle, at 111.3(5)°, is slightly opened, as often found in metal sulfur 7c-f,8,15c and phosphorus 20c,d,h,24 ylide complexes, and is assigned to steric repulsion factors. 7f,20d 3 Perspective view of the molecular structure of the cation ( 3 ) + . Thermal ellipsoids are at 50% probability.…”
Section: Resultssupporting
confidence: 73%
“…This seems to be a general trend in the reactivity of neutral nucleophiles with halo−halomethyl metal complexes. Many of these react, for example, with tertiary phosphines and give the fragments [X−M−CH 2 −PR 3 ] + X - ; moreover, the palladium complex (Me 2 S) 2 PdCl(CH 2 Cl) slowly decomposes in the air to a complex mixture also containing (Me 2 S)Pd(CH 2 SMe 2 )Cl 2 9a…”
Section: Resultsmentioning
confidence: 99%
“…However, the reverse reactivity has been observed at least once, i.e. , in the reaction of mer,cis- [(Me 3 P) 3 RhCl 2 (CH 2 Cl)] with an excess of PMe 3 , which displaces Cl - from Rh rather than RhCH 2 Cl, yielding trans -[(Me 3 P) 4 RhCl(CH 2 Cl)]Cl 20f…”
By reacting
trans-[PdCl(CH2Cl)(PBut
2H)2]
with tetrahydrothiophene (THT) or diethyl
sulfide in the presence of AgCF3SO3 or
TlPF6, the cationic palladium sulfur ylides
trans-[PdCl(CH2SR2)(PBut
2H)2]X
((2)CF3SO3 SR2 =
THT, X = CF3SO3;
(2)PF6 SR2 = THT, X
=
PF6; (3)PF6 SR2 =
SEt2, X = PF6) were isolated and
characterized. The crystal and molecular
structures of (2)CF3SO3
and (3)PF6 were solved by X-ray analyses.
The related complex
cis-[PdCl{CH2S(H)CH3}(PBut
2H)2]CF3SO3
was prepared by an independent route, i.e., by
the oxidative addition of the C−Cl bond of
Cl−CH2SCH3 to
Pd(PBut
2H)3 to form
trans-[PdCl(CH2SCH3)(PBut
2H)2],
which was then protonated with triflic acid.
“…This is an unprecedented structural arrangement for Pt II ylide complexes . The only other structurally characterized κ 1 phosphorus ylide complexes of Pt II , according to the Cambridge Structural Database, are cationic complexes that contain only one ylide ligand ( trans- [PtI(PEt 3 ) 2 (CH 2 PEt 3 )] + and cis -[PtX(PPh 3 ) 2 (CH 2 PPh 3 )] + (X = Cl, I) , ) or two ylide ligands in a relative cis arrangement ( cis -[PtI(PPh 3 )(CH 2 PPh 3 ) 2 ] + ). The complex described here, on the other hand, is neutral and features the two ylide ligands in a mutually trans arrangement.…”
The reaction of (nBu4P)2[PtBr4] with 2,2'-(C6H4Li)2 yields selectively (by 195 Pt and 31 P NMR) compound trans-PtBr2[CH(nPr)(PnBu3)]2 as a mixture of meso (R,S) and dl (R,R+S,S) diastereoisomers. The initially formed 1:1 mixture slowly evolves toward a solution richer in the meso compound, which then crystallizes selectively. In addition to the NMR characterization, the meso isomer has also been characterized by a single crystal X-ray diffraction analysis. DFT calculations in the gas phase and in solution (THF) confirm the slight thermodynamic preference for the meso isomer and reproduce the chemical shift difference of the 195 Pt NMR resonances. They also suggest the likelihood of a dissociative mechanism for the slow diastereoisomer interconversion.
“…This method is quite general and usually occurs in very mild reaction conditions. Platinum, rhodium, iron and palladium complexes (21)-(25) (Scheme 8) have been prepared, using phosphines [79][80][81][82][83], amines [84] or sulfides [85] as nucleophiles. Some of the most representative examples are shown in Scheme 8.…”
Section: Scheme 5 Ambidentate (O Vs C) Behaviour Of Stabilized Ylidesmentioning
The use of ylides of P, N, As or S as ligands toward transition metals is still a very active research area in organometallic chemistry. This fact is mainly due to the nucleophilic character of the ylides and to their particular bonding properties and coordination modes. They can behave as monodentate or bidentate-chelate or bridging-species, they can be used as chiral auxiliary reagents, they are interesting reaction intermediates or useful starting materials in a wide variety of processes, etc. The most interesting bonding properties, structural features and applications of these versatile compounds will be covered in this chapter.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
