51014-40-5

Upstream product

• 28005-97-2 [PtCl₂(propionitrile)₂] 
• 119072-54-7 2,6-dimethylphenyl isonitrile 
• 15617-14-8 cis-dichlorobis(propiononitrile)platinum(II) 
• 12080-32-9 dichloro( 1,5-cyclooctadiene)platinum(ll) 
• 12080-32-9 dichloro(1,5-cyclooctadiene)platinum(ll) 
• 21264-32-4 diacetonitriledichloridopalladium(II) 

Downstream Products

• 81205-92-7 cis-bis(2,6-xylylisocyanide)tris(2,6-xylylimino)platinacyclobutane 

Relevant academic research and scientific papers

(Isocyano Group π-Hole)???[dz2 -MII] Interactions of (Isocyanide)[MII] Complexes, in which Positively Charged Metal Centers (d8-M=Pt, Pd) Act as Nucleophiles

Inspection of the X-ray structures of the newly prepared trans-[MII(CNXyl)2(DAPT)2]Cl(BF4) (M=Pd, Pt; Xyl=2,6-Me2C6H3; DAPT=4,6-diaminopyrimidine-2(1H)-thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π-hole???metal interactions between a ligated isocyano group (acting as a π-hole donor) and the positively charged d8-PtII and d8-PdII metal centers (acting as nucleophiles); this is the first identification of π-hole???metal interactions with triple-bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π-hole???metal contacts are formed upon interaction between the electrophilic isocyano C atom (π-hole donor) and the nucleophilic dz2 orbital of the metal centers, which act as π-hole acceptors. Available CCDC data were processed from the perspective of the π-hole???metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π-hole acceptor ability.

Formation of Homo- and Heteronuclear Platinum(II) and Palladium(II) Carbene Complexes in the Reactions of Coordinated Isocyanides with Aminothiazaheterocycles

The reaction of 5-(trifluoromethyl)-1,3,4-thiadiazol-2-amine with cis-dichlorobis(2,6-dimethylphenyl isocyanide)platinum(II) (cis-[PtCl2(CNXyl)2], Xyl = 2,6-Me2C6H3) gave platinum(II) monocarbene comp

Synthesis of Mixed-Ligand Nitrileand Carbonyl–Isocyanide Complexes of Platinum(II) and Their Reaction with P-Toluenesulfonyl Hydrazide

Mixed-ligand nitrile- and carbonyl-isocyanide complexes of platinum(II) trans-[PtCl2(NCEt)CNXyl] and trans-[PtCl2(CO)CNXyl] (Xyl = 2,6-Me2C6H3) have been prepared for the first time. The compounds hav

Interplay of metallophilic interactions, π-π Stacking, and ligand substituent effects in the structures and luminescence properties of neutral PtII and PdII aryl isocyanide complexes

Packing interactions in the crystal structures of a series of cis-M(CNAr)2Cl2 complexes (M = Pt, Pd; Ar = substituted phenyl) were examined and correlated with the luminescence properties of the Pt complexes. The structures of the PhNC and p-tolyl isocyanide complexes exhibit extended chains of metallophilic interactions with M...M distances of 3.24-3.25 and 3.34 A, respectively, with nearly isostructural Pt and Pd compounds. Both structure types contain void channels running parallel to the M...M chains. The channels are 3-4 A wide and vacant for the phenyl structures, while those in the p-tolyl structures are up to 7.6 A wide and contain water. These channeled structures are stabilized by a combination of metallophilic bonding and aryl π-π stacking interactions. The Pt structure with 4-F substituents also features extended Pt...Pt chains, but with longer 3.79 A distances alternating with shorter 3.37 A contacts. Structures with 4-CF3 and 4-OMe substituents exhibit mostly isolated dimers of M...M contacts. In complexes with 2,6-dimethylphenyl isocyanide, steric hindrance precludes any short M...M contacts. The primary effect of aryl substitution is to provide alternative packing motifs, such as CF 3...π and CH3...π interactions, that either augment or disrupt the combination of metallophilic contacts and π-π stacking needed to stabilize extended M...M chains. Differences in the Pt and Pd structures containing 4-F and 4-OMe substituents are consistent with a higher driving force for metallophilic interactions for Pt versus Pd. The M-C and M-Cl bond distances indicate a slightly higher trans influence for aryl isocyanides bound to Pt versus Pd. The three extended Pt...Pt chain structures display luminescence assignable to (dσ*→pσ) excited states, demonstrating the existence of substantial orbital communication along the metal-metal chains. Face-indexing shows that the preferred crystal growth axis is along the metal-metal chains for the luminescent structures. Variable temperature structural studies showed that both M...M and π-π interactions contract upon cooling. Overall, this study suggests that synergy with π-π and other interactions is necessary to stabilize extended M...M chain structures. Thus, efforts to design functional materials based on metallophilic bonding must consider the full array of available packing motifs.

First example of an imine addition to coordinated isonitrile

The interplay between cis-[PtCl2{CNC6H3(2,6-Me2)}2] and Ph2C{double bond, long}NH results in the addition of benzophenone imine to one isonitrile ligand to yield the aminoimino-carbene cis-

Acetonyl platinum(II) complexes

Me4N[Pt{CH2C(O)Me}Cl2(η2- C2H4)] (1), reacts either (1) with neutral ligands to afford cis-Me4N[Pt{CH2C(O)Me}Cl2(L)] (L = CO (2), η2-PhCH=CH2 (3), η2-PhC=CPh (4), η2-H2C=C=CMe2 (5), PPh3 (6), AsPh3 (7)), trans- or/and cis-[Pt{CH2C(O)Me}CIL 2] (L = PPh3 (8), AsPh3 (9), tht (10), XyNC (11), 'BuNC (12), py (17)), [Pt(CH2C(O)Me)Cl(η2-C 2H4)(L)] (L = py (16)), or cIS-[Pt{CH2C(O)Me} ClL2] (L2 = norbornadiene (nbd, 18), 1,5-cyclooctadiene (cod, 19), bis(diphenylphosphino)methane (dppm, 20), 4,4′-di-tert-butyl-2, 2′-bipyridyl (dbbpy, 21)) or (2) with [Tl(acac)] to give [Pt{CH 2C(O)Me}(O,Oacac)(η2-C2H4)] (22) which reacts with neutral ligands to give [Pt{CH2C(O)Me}(O,O-acac) (L)] (L = CO (23), PPh3 (24), XyNC (25)). The different behavior of py and stronger π-acceptor ligands, as CO and PR3 toward 1, has been explained through a DFT study. Reaction of 11trans with 2 equiv of XyNC affords a mixture of trans-[Pt(C(O)NHXy JCl(CNXy)2] (13) and irans-[Pt{C(NHXy)2}Cl(CNXy)2]Cl (14). The first was isolated by recrystallization and the latter by reacting CW-[PtCl2(CNXy)2] with 2 equiv of XyNC. However, cis-[Pt{CH2C(O)Me}2(bpy)] reacts with 4 equiv of XyNC to give cis-[Pt(CH2C(O)Me)2(CNXy) 2] (15).

Low-valent Isocyanide Complexes and Clusters of Palladium and Platinum. Crystal Structure of (RNC)2> (R=2,6-Me2C6H3)

Reduction of (R=2,6-Me2C6H3) with sodium amalgam in the presence of isocyanide gave two clusters, (1a) and (2a), and two metallocycles, (RNC)2> (3a) and (RNC)2> (4a).In (2a) the six Pt atoms define a trigonal prism whose edges are associated with bridging and terminal isocyanide groups and the mercury atom is sanwiched by the two triangular Pt3 cores.The structure of (4a) was determined by X-ray analysis: space group Pbcn, a=18.542(11), b=22.702(5), c=22.197(5) Angstroem, and Z=8.In a similar reaction of (M=Pt or Pd) having bulky R groups 2,4-But2-6-MeC6H2 or 2,4,6-But3C6H2 gave the corresponding triangular trimetallic complexes .Six isocyanide molecules are bound to the metals as terminal and bridging ligands in the 2,4-di-t-butyl-6-methylphenyl isocyanide complex, and as only terminal isocyanide ligand in the 2,4,6-tri-t-butylphenyl isocyanide.Emission spectra of (2a) and the triangular palladium complexes were measured at 77 K; the former showed a fluorescence band at ca. 720 nm and the latter a phosphorescence band at ca. 640 nm.