144717-70-4Relevant academic research and scientific papers
New metal-only Lewis pairs: Elucidating the electronic influence of N -heterocyclic carbenes and phosphines on the dative Pt-Al bond
Bauer, Juergen,Bertermann, Ruediger,Braunschweig, Holger,Gruss, Katrin,Hupp, Florian,Kramer, Thomas
, p. 5617 - 5626 (2012)
The synthesis and full characterization of a new heteroleptic N-heterocyclic carbene (NHC)-phosphine platinum(0) complex and formation of its corresponding alane adduct is reported. The influence of the ligands on the Lewis basic properties was studied vi
A B-C double bond unit coordinated to platinum: An alkylideneboryl ligand that is isoelectronic to neutral aminoborylene ligands
Brand, Johannes,Braunschweig, Holger,Hupp, Florian,Phukan, Ashwini K.,Radacki, Krzysztof,Sen, Sakya S.
, p. 2240 - 2244 (2014/03/21)
The reaction of [Pt(PCy3)2] with Br 2B-CH(SiMe3)2 resulted in generation of the first alkylideneboryl complex, trans-[Br(Cy3P)2Pt{B= CH(SiMe3)}], with concomitant elimination of Me3SiBr. The trans bromide ligand of the alkylideneboryl complex was readily substituted by a methyl group upon treatment with methyllithium, leading to another alkylideneboryl complex, trans-[Me(Cy3P)2Pt{B=CH(SiMe 3)}]. Various spectrochemical techniques, single-crystal X-ray crystallography, and quantum chemical calculations confirmed the formulation of a double bond between the boron and the carbon atom. The theoretical studies also provided evidence for the stronger trans influence of the alkylideneboryl ligand over iminoboryl and oxoboryl ligands. Copyright
Contrasting reactivity of fluoropyridines at palladium and platinum: C-F oxidative addition at palladium, P-C and C-F activation at platinum
Jasim, Naseralla A.,Perutz, Robin N.,Whitwood, Adrian C.,Braun, Thomas,Izundu, Joseph,Neumann, Beate,Rothfeld, Sascha,Stammler, Hans-Georg
, p. 6140 - 6149 (2008/10/09)
The divergent behavior of palladium(0) and platinum(0) is revealed in the reactivity of [M(PR3)2] (M = Pd or Pt; R = Cy or iPr) toward pentafluoropyridine and 2,3,5,6-tetrafluoropyridine. The palladium complexes react with pentafluoropyridine at 100 °C to yield the fluoride complexes trans-[Pd(F)(4-C5NF4)(PR 3)2]. They do not react with 2,3,5,6-tetrafluorapyridine. The reaction of platinum(0) complexes [Pt(PR3)2] with pentafluoropyridine in THF at ambient temperature yields trans-[Pt(R)4-C 5NF4)(PR3)(PFR2)] complexes, whereas the reaction of [Pt(PCy3)2] with 2,3,5,6- tetrafluoropyridine results in C-H activation to form cis-[Pt(H)(4-C 5NF4)(PCy3)2]; this complex may be converted to the trans isomer by photolysis. The cis-hydride also forms during the reaction of [Pt(PCy3)2] with C5NF 5 in hexane. These reactions also contrast with earlier studies of the reactivity of the same substrates toward {Ni(PEt3)2}, which yield [Ni(F)(2-C5NF5)(PEt3)2] with pentafluoropyridine and [Ni(F)-(2-C5NF4H)(PEt 3)2] with tetrafluoropyridine. Thus palladium has different regioselectivity from nickel and is the least reactive. Platinum is capable of both C-F and C-H activation and is alone in the triad in undergoing rearrangement to the alkyl complex with the fluorophosphine ligand. Mechanisms for the rearrangement are proposed. The platinum dihydride complex trans-[Pt(H)2(PR3)2] reacts with pentafluoropyridine at room temperature, yielding a 1:1:1 mixture of trans-[PtH(FHF)(PR3)2], trans-[Pt(H)(4-C 5NF4)(PR3)2], and trans-[Pt(R)(4-C5NF4)(PR3)(PFR2)]. Crystal structures are reported for trans-[Pd(F)(4-C5NF 4)-(PCy3)2]-H2O-C6H 6, trans-[Pd(F)(4-C5NF4)(PiPr 3)2], trans-[Pt(C6H11)(4-C 5NF4)(PCy3)(PFCy2)]-CH 2Cl2, and cis-[Pt(H)(4-C5NF4) (PCy3)2].
Preparation and structural characterization of transition metal complexes featuring the ferrocenyl(bromo)boryl ligand
Braunschweig, Holger,Radacki, Krzysztof,Rais, Daniela,Seeler, Fabian
, p. 5545 - 5549 (2008/10/09)
Transition metal complexes that feature the ferrocenyl(bromo)boryl ligand, -B(Fc)Br, were prepared utilizing salt-elimination and B-Br bond oxidative addition strategies. The stabilizing interaction that causes bending of the boron atom toward the ferrocenyl iron center in the FcBBr2 precursor (1) weakens upon coordination of boron to the [(η5-C 5R5)-(OC)2Fe] and trans-[(Cy3P) 2PtBr] fragments. The efficient π-back-bonding capability of the latter is reflected in the absence of any Fe-B interaction in crystalline trans-[(Cy3P)2Pt-(Br){B(Fc)Br}] (7), the first platinum haloboryl complex featuring a non-heteroatom-stabilized boryl ligand to be fully characterized and structurally authenticated. In the half-sandwich complexes [(η5-C5R5)(OC)2Fe{B(Fc)Br}] (R = H, 2; R = Me, 3) different relative orientations of the [(η5- C5R5)(OC)2Fe] and -B(Fc)Br groups are accompanied by different degrees of bending within the boryl ligand. The sensitivity of this parameter to the electronic environment at boron offers an indirect qualitative estimation of the π-bonding component of the TM-B bond.
Investigations of the Factors Affecting the Stability of Dihydrogen Adducts of Platinum(II)
Stahl, Shannon S.,Labinger, Jay A.,Bercaw, John E.
, p. 2422 - 2431 (2008/10/08)
The preparation and study of Pt(II) H2 adducts and Pt(IV) dihydride complexes are described. The species of interest are generated by protonation of hydridoplatinum(II) complexes of the type trans-(PCy3)2Pt(H)X [X = SiHsu
