111139-95-8

Basic information

• Product Name: trans-{(PPh₃)2Pd(CN(C₆H₄-p-Me)CH₂CH₂N(H))Br}BF₄
• CAS NO: 111139-95-8
• Molecular Weight: 957.929
• Mol File: 111139-95-8.mol
• Article Data: 1

Chemical Properties

• CAS DataBase Reference: trans-{(PPh₃)2Pd(CN(C₆H₄-p-Me)CH₂CH₂N(H))Br}BF₄(CAS DataBase Reference)
• NIST Chemistry Reference: trans-{(PPh₃)2Pd(CN(C₆H₄-p-Me)CH₂CH₂N(H))Br}BF₄(111139-95-8)
• EPA Substance Registry System: trans-{(PPh₃)2Pd(CN(C₆H₄-p-Me)CH₂CH₂N(H))Br}BF₄(111139-95-8)

Safety Data

• Hazardous Substances Data: 111139-95-8(Hazardous Substances Data)

Upstream product

• 13755-29-8 sodium tetrafluoroborate 
• 109-72-8 n-butyllithium 
• 110313-88-7 trans-{(PPh₃)2Pd(CNC₆H₄-p-Me)Cl}BF₄ 
• 2576-47-8 2-bromoethylamine hydrobromide 

Relevant articles and documents

Transition-metal-promoted cyclization reactions of isocyanide ligands. Synthesis of cyclic diaminocarbenes from isocyanide complexes of palladium(II) and platinum(II) and X-ray structure of cis-Br2Pt[CN(C6H4-p-Me)CH2CH 2N(H)](PPh3)

Electrophilic isocyanide ligands in cationic Pt(II) and Pd(II) complexes of the type trans-[L2M(CNR)X]BF4 (I) (L = phosphine; R = alkyl, aryl; X = halide, Me) are converted to the five-membered cyclic diaminocarbene derivatives trans-{L2M[CN(R)-CH2CH2N(H)]X}BF4 (II) by reaction with 2-bromoethylamine hydrobromide in the presence of n-BuLi. 2-Bromoethylamine reacts also with one or even two RNC ligands in neutral complexes of the type cis-Cl2Pt(CNC6H4-p-Me)(PPh3) and cis-Cl2Pd-(CNC6H4-p-Me)2 to form the corresponding mono- and bis(diaminocarbene) derivatives cis-Br2Pt[CN(C6H4-p-Me)-CH2CH 2N(H)](PPh3) and cis-Br2Pd[CN(C6H4-p-Me)CH2CH 2N(H)]2, respectively. It is suggested that such reactions proceed by nucleophilic attack of 2-bromoethylamine on the metal-bound isocyanide carbon atom to form an imido intermediate which cyclizes intramolecularly to give the carbene products II. The Pt(II)- and Pd(II)-cyclic diaminocarbene complexes were characterized by their elemental analysis and IR and 1H and 31P NMR spectra. The structure of cis-Br2Pt[CN(C6H4-p-Me)-CH2CH 2N(H)](PPh3) was established by an X-ray diffraction study. The structural model was refined to R = 0.029 (Rw, = 0.030) for 2930 independent reflections. Crystal data: triclinic, space group P1, a = 11.255 (3) ?, b = 13.393 (2) ?, c = 10.020 (2) ?, α = 106.55 (1)°, β = 112.00 (4)°, γ = 76.99 (3)°, Z = 2. The angle formed between the platinum square plane and the carbene ligand is 102.1°. The cyclic diaminocarbene ligand is strictly planar with C(sp2)-N(1) and C(sp2)-N(2) bond lengths of 1.34 (1) and 1.36 (1) ?, indicating extensive π-bonding between the nitrogen atoms and the carbene carbon. The N-H group in II can be deprotonated by n-BuLi to give the imino intermediate trans-{L2M[CN(R)CH2CH2N:]X}BF4, which rapidly reacts with electrophiles such as allyl bromide and propargyl bromide to give the new functionalized carbenes trans-{L2M[CN(R)-CH2CH2N-CH 2CH=CH2]X}BF4 (M = Pd, Pt) and trans-{L2M[CN(R)CH2CH2N-CH 2C≡CH]X}BF4 (M = Pt).