Advances on supramolecular assembly of cyclometalated platinum(Ⅱ) complexes

Organoplatinum(Ⅱ) compounds have received enormous attention over the past decades due to their square-planar geometry as well as intriguing photo-physical properties.Self-assembly has emerged as an excellent approach to create well-ordered supramolecular architectures with tunable properties,which underpin the role of solvent-directed approach for the design of functional materials.In this minireview,the recent advances on supramolecular self-assembly of cyclometalated platinum(Ⅱ) complexes have been discussed.During the self-assembly process,non-covalent Pt-Pt and π-π interactions play crucial roles in controlling the structures and functions of the resulting assemblies.     

A shotgun approach for the identification of platinum–protein complexes

A shotgun approach including peptide-based OFFGEL-isoelectric focusing (IEF) fractionation has been developed with the aim of improving the identification of platinum-binding proteins in biological samples. The method is based on a filter-aided sample preparation (FASP) tryptic digestion under denaturing and reducing conditions of cisplatin–, oxaliplatin–, and carboplatin–protein complexes, followed by OFFGEL-IEF separation of the peptides. Any risk of platinum loss is minimized throughout the procedure due to the removal of the reagents used after each stage of the FASP method and the absence of thiol-based reagents in the focusing buffer employed in the IEF separation. The platinum–peptide complexes stability after the FASP digestion and the IEF separation was confirmed by size exclusion chromatography-inductively coupled plasma-mass spectrometry (SEC-ICP-MS). The suitability of peptide-based OFFGEL-IEF fractionation for reducing the sample complexity for further nano-liquid chromatography-electrospray ionization-tandem mass spectrometry (nLC-ESI-MS/MS) analysis has been demonstrated, allowing the detection of platinum-containing peptides, with significantly lower abundance and ionization efficiency than unmodified peptides. nLC-MS/MS analysis of selected OFFGEL-IEF fractions from tryptic digests with different complexity degrees: standard human serum albumin (HSA), a mixture of five proteins (albumin, transferrin, carbonic anhydrase, myoglobin, and cytochrome-c) and human blood serum allowed the identification of several platinum–peptides from cisplatin–HSA. Cisplatin-binding sites in HSA were elucidated from the MS/MS spectra and assessed considering the protein three-dimensional structure. Most of the potential superficial binding sites available on HSA were identified for all the samples, including a biologically relevant cisplatin-cross-link of two protein domains, demonstrating the capabilities of the methodology.

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Graphical Abstract Graphical abstract shows the several steps involved in the identification of platinum-protein complexes: FASP digestion of proteins, peptide fractionation by OFFGEL-IEF and identification of Pt-complexes by nLC-ESIMS/MS

     

Coordination chemistry of silones: Synthesis and reactivity of new silicon-disubstituted (η4-silole) complexes

The synthesis of some new silicon-disubstituted (η⁴-2,5-diphenylsilacyclopentadiene)tricarbonyliron complexes are described. Stable complexes with various functional groups attached at silicon have been isolated. The exo position shows an enhanced reactivity, and cleavage of an SiH bond at this position occurs selectively with retention.     

SO2-binding properties of cationic η6,η1-NCN-pincer arene ruthenium platinum complexes: spectroscopic and theoretical studies

The SO(2)-binding properties of a series of η(6),η(1)-NCN-pincer ruthenium platinum complexes (NCN = 2,6-bis[(dimethylamino)methyl]phenyl anion) have been studied by both UV-visible spectroscopy and theoretical calculations. When an electron-withdrawing [Ru(C(5)R(5))](+) fragment (R = H or Me) is η(6)-coordinated to the phenyl ring of the NCN-pincer platinum fragment (cf. [2](+) and [3](+), see Scheme 1), the characteristic orange coloration (pointing to η(1)- SO(2) binding to Pt) of a solution of the parent NCN-pincer platinum complex 1 in dichloromethane upon SO(2)-bubbling is not observed. However, when the ruthenium center is η(6)-coordinated to a phenyl substituent linked in para-position to the carbon-to-platinum bond, i.e. complex [4](+), the SO(2)-binding property of the NCN-platinum center seems to be retained, as bubbling SO(2) into a solution of the latter complex produces the characteristic orange color. We performed theoretical calculations at the MP2 level of approximation and TD-DFT studies, which enabled us to interpret the absence of color change in the case of [2](+) as an absence of coordination of SO(2) to platinum. We analyze this absence or weaker SO(2)-coordination in dichloromethane to be a consequence of the relative electron-poorness of the platinum center in the respective η(6)-ruthenium coordinated NCN-pincer platinum complexes, that leads to a lower binding energy and an elongated calculated Pt-S bond distance. We also discuss the effects of electrostatic interactions in these cationic systems, which also seems to play a destabilizing role for complex [2(SO(2))](+).     

η3-Propargyl complexes of molybdenum, tungsten, and rhenium

The reactions of the Me _n C₆H_6−n M(CO)₃ (M=Cr, Mo, W;n=3, 5, 6) and C₅R₅M(CO)₃ (M=Mn, Re; R=H, Me) complexes with propargyl alcohol in acidic media under UV irradiation were studied. Novel Me _n C₆H_6−n M(CO)₂(η³-C₃H₃)BF₄ (M=Mo, W;n=3, 5, 6) and C₅R₅Re(CO)₂(η³-C₃H₃)CF₃SO₃ complexes with the 3ē-propargyl ligand were synthesized, and their properties compared with those of similar η³-allyl derivatives. The structure and dynamic propeties of the compounds obtained are discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1796–1803, September, 1999.     

Reactivity of hydroxo palladium and platinum complexes towards N-substituted salicylaldimines and β-ketoimines

The binuclear hydroxo complexes [{M(C6F5)2(OH)}2]2–(M=PdandPt)reactwithN-substituted salicylaldimines (HSal=NR) or -ketoimines (RN=CMeCH2COR) to give the corresponding N-substituted salicylaldiminato or -ketoiminato mononuclear complexes, [M(C6F5)2(Sal=NR)]– (M=Pd or Pt; R= Me, Et, Ph, o-MeC6H4, p-MeC6H4 or p-ClC6H4) or [(C6F5)2M{N(R)C(CH3)CHC(O)R}]– (M=Pd or Pt; R=o-MeC6H4 or p-MeC6H4; R=Me or Ph), respectively. The complexes have been characterized by partial elemental analyses, conductance measurements and spectroscopic (i.r. and 1H and 19F- n.m.r.) methods.     

Synthesis and reactions of dicarbonyl (η2-indene)-η5-indenyl complexes of manganese and rhenium

Photochemical reactions of M(CO)₃(⁵-C₉H₇), where M=Mn (1) or Re (2), with indene have produced ²-indene complexes M(CO)₂(²-C₉H₈)(⁵-C₉H₇), where M=Mn (3) or Re (4). Deprotonation of complex3 witht-BuOK in THF at –60 °C gives the anion [Mn(CO)₂(¹-C₉H₇)(⁵-C₉H₇)^– (5), in which there occurs a rapid interchange of the Mn(CO)₂(⁵-C₉H₇) group between positions 1 and 3 in the ¹-indenyl ligand. The reaction of complex4 with Ph₃CPF₆ in CH₂Cl₂ at 0 °C leads to the complex [Re(CO)₂(³-C₉H₇)(⁵-C₉H₇)PF₆, whereas the similar reaction of complex3 gives only decomposition products even at –20 °C.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1280–1285, July, 1993.     

Insertion of alkynes into the heterocycle of (η-pentaalkyl-2,3-dihydro-1,3-diborolyl)(η-pentamethylcyclopentadienyl)ruthenium: Formation and characterization of 4-borataborepine ruthenium complexes

The violet ruthenium complex [(η⁵-C₅Me₅)Ru(η⁵-C₃B₂Me₄R¹)] (2a, R¹ = Me) reacts with terminal alkynes R²CCH to give yellow 4-borataborepine compounds [(η⁵-C₅Me₅)Ru{η⁷-(MeC)₃(R¹B)₂(R²C₂H)}] (4c, R¹ = Me, R² = Ph; 4d, R¹ = Me, R² = SiMe₃; 4e, R¹ = Me, R² = H). The insertion of alkynes into the folded C₃B₂ heterocycle of 2a causes some steric hindrance, which yields with elimination of the distant boranediyl group the corresponding boratabenzene complexes 5 as byproducts. The analogous reactions with internal alkynes R²CCR² proceed slowly and afford predominantly the boratabenzene complexes [(η⁵-C₅Me₅)Ru{η⁶-(MeC)₃(MeB)(R²C)₂}] (5f, R² = Et, 5g, R² = p-tolyl), respectively. In the latter case, three byproducts are formed: methylboronic acid and 1,2,3,4-tetra-p-tolyl-1,3-butadiene (9) due to hydrolysis of the postulated 2,3,4,5-tetra-p-tolyl-1-methylborole (10) and unexpectedly, the cationic triple-decker complex [{(η⁵-C₅Me₅)Ru}₂{μ,η⁷-(MeC)₃(MeB)₂(CH)₂}]Cl (11) having two separated CH groups. The new compounds were characterized by NMR, MS, and single-crystal X-ray studies of 4c, 5f, 9 and 11.     

μ-η6,η6-Arene-bridged diuranium hexakisketimide complexes isolable in two states of charge

Diuranium μ-η(6),η(6)-arene complexes supported by ketimide ligands were synthesized and characterized. Disodium or dipotassium salts of the formula M(2)(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (M = Na or K, Mes = 2,4,6-C(6)H(2)Me(3)) and monopotassium salts of the formula K(μ-η(6),η(6)-arene)[U(NC(t)BuMes)(3)](2) (arene = naphthalene, biphenyl, trans-stilbene, or p-terphenyl) were both observed. Two different salts of the monoanionic, toluene-bridged complexes are also described. Density functional theory calculations have been employed to illuminate the electronic structure of the μ-η(6),η(6)-arene diuranium complexes and to facilitate the comparison with related transition-metal systems, in particular (μ-η(6),η(6)-C(6)H(6))[VCp](2). It was found that the μ-η(6),η(6)-arene diuranium complexes were isolobal with (μ-η(6),η(6)-C(6)H(6))[VCp](2) and that the principal arene-binding interaction was a pair of δ bonds (total of 4e) involving both metals and the arene lowest unoccupied molecular orbital. Reactivity studies have been carried out with the mono- and dianionic μ-η(6),η(6)-arene diuranium complexes, revealing contrasting modes of redox chemistry as a function of the system's state of charge.     

Vibrational spectroscope of complexes of platinum(0)—I. Tetrakis(triphenylphosphine)platinum(0) and Dioxygenbis(triphenylphosphine)platinum(0)

Assignment of i.r. and Raman spectra for Pt(PPh₃)₄ and Pt(O₂)(PPh₃)₂ yielded values for νPtP of 137 and 157 cm⁻¹ (Pt(PPh₃)₄); 132 (antisymmetric) and 145 cm⁻¹ (symmetric) (Pt(O₂)(PPh₃)₂). For the dioxygen complex, solution phase Raman spectra gave values for both ν PtO₂ modes for the first time. Data from the ¹⁶O₂, ¹⁶O¹⁸O and ¹⁸O₂ isotopomers were used in a normal coordinate analysis of the PtO₂ fragment. The OO stretching force constant (3.0 mdyn Å⁻¹) is consistent with extensive net π-back-donation into the π* m.o.s of the O₂ ligand.     

Hydro- and chloro-substituted silyl- and silyl-η-amido-η-tetramethylcyclopentadienyl titanium complexes

Chlorosilyl-cyclopentadienyl titanium precursors [Ti(η⁵-C₅Me₄SiMeXCl)Cl₃] (X=H 2, Cl 3) were prepared by reaction of TiCl₄ with the trimethylsilyl derivatives of the corresponding cyclopentadienes. Methylation of these compounds with MgClMe under appropriate conditions afforded the methyl complexes [Ti(η⁵-C₅Me₄SiMe₂R)XMe₂] (R=H, X=Cl 5, Me 6; R=X=Me 7). Reactions of 2 and 3 with two equivalents of LiNH^tBu afforded the ansa-silyl-η-amido compounds [Ti{η⁵-C₅Me₄SiMeX(η¹-N^tBu)}Cl₂] (X=H 8, Cl 9). Methylation of 8 gave [Ti{η⁵-C₅Me₄SiMeH(η¹-N^tBu)}Me₂] 10. Complex 9 was also obtained by reaction of 8 with BCl₃, whereas the same reaction using alternative chlorinating agents (TiCl₄, HCl) resulted in deamidation to give 2, which was also converted into 3 by reaction with BCl₃. All of the new compounds were characterized by NMR spectroscopy and the molecular structures of 2 and 4 were determined by X-ray diffraction methods.     

Heterometallic binuclear complexes involving the mercury—platinum bond as a source of a platinum carbenoid in reactions with fullerene-60

The cleavage of two σ-bonds and the formation of a metallocomplex, (η²-C₆₀)Pt(PPh₃)₂, occur in a new reaction between fullerene-60 and binuclear heterometallic compounds having a mercury-platinum bond (retro-insertion promoted by C₆₀). One of these,trans- Ph₂CHCH₂HgPt(PPh₃)₂Br,1, which contains an electron-donating group at the mercury atom, reacts two orders of magnitude faster thancis-(CF₃)₂CFHgPt(PPh₃)₂CH=CPh₂,2, which has an electron-withdrawing substituent at mercury. An asymmetrical organomercury compound is the second product of the reaction. The reactants and products have been characterized by spectroscopic data (¹H,³¹P NMR, UV-VIS) and elemental analyses. Compound 2, which is more stable to retro-insertion, gives a Pt-centered free radical upon photolysis. This was used for the free-radical functionalization of C₆₀. The platinumfullerenyl radicalcis-C₆₀Pt(PPh₃)₂R² was identified by EPR spectroscopy.     

Enhancing single-molecule conductance of platinum (Ⅱ) complexes through synergistic aromaticity-assisted structural asymmetry

Seeking the strategies of designing highly conductive molecular structures is one of the core researches in molecular electronics.As asymmetric structure has manifested feasible properties in comprehensive fields, we introduce the structures of asymmetric platinum(Ⅱ) complexes into the charge transport study at single-molecule scale for the first time. The single-molecule conductance measurement results reveal that, in platinum(Ⅱ)-aryloligoynyl structures, the conductance of asymmetrically coordinated complexes is obviously higher than that of the symmetric isomers with the same molecular length, while the conductance is almost identical in symmetric and asymmetric platinum(Ⅱ)-oligoynyl complexes. Theoretical study uncovers that, upon connecting to the oligoynyl structure, the aromatic group effectively extends the π-system of the whole conductive backbone and gathers the HOMO population mainly on the longer oligoynyl ligand, which reduces the energy barrier in electron transport and enhances the conductance through HOMO energy lifting. This result provides feasible strategy for achieving high conductive molecular devices.     

Synthesis,characterization, and cytotoxicity of mixed-ligand complexes of platinum(II) with 2,2′-bipyridine and 4-toluenesulfonyl-L-amino acid dianion

Five new platinum(II) complexes (1–5) with 4-toluenesulfonyl-L-amino acid dianion and 2,2′-bipyridine (bipy) have been synthesized and characterized by elemental analysis, IR, UV, ¹H-NMR, ¹³C-NMR, and mass spectra. The crystal structure of 1 has been determined by X-ray diffraction analysis. Cytotoxicity was tested by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and sulforhodamine B (SRB) assays. The results indicate that 1–5 exert cytotoxic effects with selectivity against tested carcinoma cell lines; 5 displays better cytotoxicity against BGC-823, Bel-7402, and KB cell lines, while 1 has better cytotoxicity against KB cell line. The 4-toluenesulfonyl- L-amino acid dianions have important effects on cytotoxicity; when 4-toluenesulfonyl-L-amino acid dianions are 4-toluenesulfonyl-L-glycine and 4-toluenesulfonyl-L-phenylalanine, the complexes show better cytotoxicity.     

Electron-transfer induced cleavage and formation of C-H-bonds in 17ē and 19ē platinum complexes

The electrochemical behavior of platinum complexes [Pt(⁴-diene)(⁵-C₅R₅)]⁺BF₄ ^– (1 ⁺, diene = C₅Me₅H, R = H;2 ⁺, diene = C₅Me₅H, R = Me;3 ⁺, diene = C₆H₈, R = Me;4 ⁺, diene = C₈H₁₂, R = Me) was studied by cyclic voltammetry. Complexes1 ⁺ and2 ⁺ are shown to be capable of both oxidation and reduction. One-electron reduction of2 ⁺ gives a mixture of two neutral isomeric complexes5a,b of ³-allylic and ,,-olefinic type due to the cleavage of C-H bonds in the methyl groups of the pentamethylcyclopentadiene ligand of 19 complexes2. The preparative electrochemical oxidation of2 ⁺ results in cleavage of the C-H bond at the sp³-hybridized pentamethylcyclopentadiene carbon atom in 17 dication radical2 ²⁺ to give the decamethylplatinocene dication [Pt(⁵-C₅Me₅)₂]²⁺(BF₄)₂ (7 ²⁺). It is shown that one-electron reduction of7 ²⁺ and one-electron oxidation of5a,b is accompanied by the formation of C-H bonds to form2 ⁺.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1153–1157, June, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 94-03-08598).     

Reactions of platinum σ-acetylide complexes with dicobalt octacarbonyl: Conversion of an alkyne unit into cyclopentenone

Summary Treatment of platinum -acetylide complexes trans-Pt(PR₃)₂(569-01569-02)₂ (1) with two equivalents of Co₂(CO)₈ gave complexes trans-Pt(PR₃)₂(568-03₂-[Co₂(CO)₆]R)₂ (3) and (4), where R = Et or n-Bu and R = H or SiMe₃, in high yields. The unsubstituted platinum-alkyne-cobalt complex (i.e. R = H) reacted with alkenes (norbornylene or cyclopentene) to produce new platinum acetylides containing 2-cyclopentenone groups. All new compounds were characterized by i.r., u.v.-vis. and n.m.r. (¹H, ³¹P, ¹³C) spectroscopies.     

Electrochemical properties of 2,2":6",2″-terpyridine complexes of platinum(ii) with arenethiolate ligands. Alkylation of reduced forms of the complexes

Three mixed-ligand terpyridine-thiolate Pt^II complexes containing 2,2":6",2-terpyridine (tpy) and para-substituted thiophenolate ions, [(tpy)Pt(SC₆H₄-4-X)]BF₄ (X = NMe₂, H, NO₂) were synthesized. The complexes were isolated as chlorides or tetrafluoroborates and characterized by electrochemistry, visible electronic spectroscopy and ¹H NMR spectroscopy, and elemental analysis. Remarkable influence of the electron-donating/withdrawing properties of the substituent in the thiolate ligand on the physicochemical properties of the complexes, in particular, on the electrochemical reduction potentials, was found. The reduced forms of the complexes undergo electrochemically initiated alkylation with alkyl halides, resulting in the formation of Pt alkyl compounds.     

Dimeric uranium complexes with bridging phospholyl ligands. Crystal structure of [{U(η5-C4Me4P)(μ-η5-C4Me4P)(BH4)}2]

In the symmetrical crystal structure of [{U(η⁵-C₄Me₄P)(μ-η⁵,η¹-C₄Me₄P)(BH₄)}₂], the U-P bond distances for the terminal and bridging η⁵-phospholyl ligands are 2.945(3) and 2.995(3) Å respectively, and the U-P (η¹-phospholyl) bond length is equal to 2.996(3) Å; the tridentate borohydride ligands are cis to the (UP)₂ ring. The cis and trans isomers of [{U(Cp¹)(μ-η⁵,η¹C₄ Me₄P)(BH₄)}₂] (Cp¹ = η⁵-C₅Me₅) are in equilibrium in toluene.