Synthesis,characterization and initial biological studies of a new platinum(II) complex with deoxyalliin

A new platinum(II) complex with deoxyalliin was synthesized and characterized by chemical and spectroscopic techniques. Elemental and mass spectrometry analyses of the solid complex fit to the composition [Pt(C₆H₁₁NO₂S)Cl₂]·H₂O. ¹³C NMR, ¹⁵N NMR and infrared spectra of the complex are consistent with coordination of deoxyalliin to Pt(II) through the nitrogen and sulfur atoms forming a square-planar geometry. The complex is soluble in dimethylsulfoxide. Biological analysis for evaluation of a potential cytotoxic effect of the complex was performed using HeLa cells, a human cervix adenocarcinoma-derived cell line. The results were compared with those of a palladium(II) complex previously described.     

Synthesis and characterization of a new platinum(II) complex with L-mimosine

Synthesis and characterization of a new Pt(II)–mimosine complex are described. Elemental, mass spectrometry and thermal analyses for the complex are consistent with the formula [PtCl₂(C₈H₁₀N₂O₄)]·1.5H₂O. ¹³C NMR, ¹⁵N NMR and infrared spectroscopy indicate coordination of the ligand to Pt(II) through the N and O atoms in a square-planar geometry. The final residue after thermal treatment was identified as metallic Pt. The complex is soluble in dimethylsulfoxide.     

Synthesis,spectroscopic characterization,and antibacterial assays in vitro of a new platinum(II) complex with methionine sulfoxide

A new platinum(II) complex with methionine sulfoxide was synthesized and characterized by chemical and spectroscopic techniques. Elemental analyses, mass spectrometric measurements (electrospray ionization quadrupole time-of-flight mass spectrometry), and thermal analyses of the solid compound fit the composition [(C₅H₁₀NO₃S)Pt(µ-Cl)₂Pt(C₅H₁₀NO₃S)]?·?2.5H₂O. Infrared spectroscopic data indicate coordination of the ligand to Pt(II) through the nitrogen of NH₂ and the sulfur of the S=O group. ¹H-¹⁵N nuclear magnetic resonance spectroscopic data confirm nitrogen coordination. Antibacterial activities were evaluated by antibiogram assays using the disc diffusion method. The platinum(II) complex showed antibacterial activity against Gram-negative Pseudomonas aeruginosa bacterial cells.     

cis‐Dichloro(dimethyl sulfoxide‐S)(2‐methoxypyridine‐N)platinum(II)

The title complex, [PtCl₂(C₆H₇NO)(C₂H₆OS)], exhibits square‐planar geometry. The plane of the pyridine ring makes a dihedral angle of 67.2 (3)° with the square plane of the metal center. The S—O bond is nearly aligned with the adjacent Pt—N bond, leaving the methyl groups of the di­methyl sulfoxide ligand to stagger the Pt—Cl bond.     

The Synthesis of Mono- and Bi-Metallic Platinum(II) and/or (IV) Complexes Containing the Ligand Bis(diphenylphosphino) Methylamine

Complexes of the type [Pt R₂ (dppma-PP′)] (R─Me, Et, Ph, CH₂Ph, C₆H₄ Me-p, C₆H₄OMe-2, CH₂CMe₃, 1-naphthyl, C₆H₄Me-o, dppma = Ph₂PNMe PPh₂) have been prepared from [PtCl₂, (dppma-PP′)] and the corresponding alkyl-lithium or Grignard reagents. Equilibrium constants, k, for the conversion of [PtR₂ (dppma-PP′)] into cis-[PtR₂(dppma-P)₂] with dppma were studied using ³¹P NMR spectroscopy at room temperature. Equilibrium is rapidly established for R─C₆H₄-Me-o, at 20°C. Complex of the type cis-[PtR₂ (dppma-P)₂] was isolated R─C₆H₄ Me-o. The complexes [PtMe₂(dppma-P)₂] and [Pt(o-methoxyphenyl)₂(dppma-P)₂] were prepared, but unfortunately decomposed once isolated, the only evidence for its formation being from ³¹P-{¹H} NMZR spectroscopy. The o-tolyl or 1-naphthyl complexes exist as syn-anti mixtures in solution, due to restricted rotation around the platinum aryl bonds. Treatment of several complexes of the type [PtR₂(dppma-PP′)] with MeI gives [PtR₂Me(I)(dppma-PP′)] with trans addition of MeI. Treatment of [PtR₂(dppma-PP′)] with HCl gives [Pt Cl (R) (dppma-PP′)] for R─C₆H₂Me₃-2,4,6, C₆H₄-CH₃-2, C₆H₄-Me-4, Me, 1-naphthyl. The ¹H, ³¹P NMR parameters for these complexes are discussed. Attempted preparation of complexes of the type [PtR₂ (dppma-P)₂M] (R─C₆H₄-Me-2, Me CN-C₆H₄-Me-4); M─Pd, Pt, Au,) are reported.     

Darstellung,spektroskopische Charakterisierung und Kristallstrukturen von [(C5H5N)2CH2][PtCl5(SCN)] und cis-[(C5H5N)2CH2][PtCl4(SCN)2]

Preparation, Spectroscopic Characterization, and Crystal Structures of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] and cis -[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] By treatment of [PtCl₆]^2– with SCN^– in aqueous solution a mixture of chlorothiocyanatoplatinates(IV) is formed, from which [PtCl₅(SCN)]^2– and cis-[PtCl₄(SCN)₂]^2– have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations on single crystals of [(C₅H₅N)₂CH₂][PtCl₅(SCN)] ( 1 ) (tetragonal, space group P 4₃, a = 7.687(1), c = 29.698(4), Z = 4) and cis-[(C₅H₅N)₂CH₂][PtCl₄(SCN)₂] ( 2 ) (monoclinic, space group P 2₁/n, a = 11.2467(9), b = 15.0445(10), c = 11.3179(13), β = 92.840(9)°, Z = 4) show, that the thiocyanate groups are coordinated via S atoms with average Pt–S distances of 2.339 Å and Pt–S–C angles of 104.7° up to 107.1°. Using the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra have been assigned by normal coordinate analyses. The valence force constants of the S–Pt–Cl˙ axes are f_d(PtS) = 1.81 ( 1 ) and 1.87 ( 2 ), f_d(PtCl ^× ) = 1.77 ( 1 ) and 1.81 ( 2 ), of the Cl–Pt–Cl axes are f_d(PtCl) = 1.93 ( 1 ) and 1.90 mdyn/Å ( 2 ). The ¹⁹⁵Pt NMR spectra from dichlormethane solutions exhibit each one sharp signal at 3975.6 ( 1 ) and 3231.6 ppm ( 2 ), respectively.     

Chemical and spectroscopic studies of a new palladium(II) complex with N -acetyl-L-cysteine

Chemical and spectroscopic studies of a new palladium(II) N-acetyl-L-cysteine complex are described. Elemental analyses for the solid complex are consistent with the formula [Pd(C₅H₈NO₃S)₂]?·?H₂O or [Pd(NAC)₂]?·?H₂O. Solid-state ¹³C nuclear magnetic resonance (NMR), UV–Visible (UV–Vis) and infrared (IR) spectroscopic analyses are consistent with coordination of the ligand to palladium(II) through the nitrogen and sulfur atoms in a square-planar geometry. Thermogravimetric and differential thermal analyses confirmed the composition; final residue was identified as metallic palladium.     

Synthesis,characterization, and solution behavior of mercury(II) chloride complexes with phosphine tellurides

The reaction of mercury(II) chloride with neutral phosphine telluride ligands (R₃PTe) produced new mercury(II) complexes, HgCl₂(R₃PTe)₂ [R = Me₂N (1), Et₂N (2), C₄H₈N (3), C₅H₁₀N (4) or ^n-Bu (5)]. Attempts to isolate the complex of HgCl₂ with the morpholinyl ligand, (OC₄H₈N)₃PTe, were unsuccessful. Complexes 1–5 have been characterized by elemental analyses, IR, and multinuclear (³¹P, ¹²⁵Te, and ¹⁹⁹Hg) NMR spectroscopy. The solution behavior of the complexes was investigated using variable temperature NMR spectroscopy in the presence of excess ligand and indicated fast ligand exchange on the NMR timescale at room temperature. The metal–ligand exchange barriers in these complexes were estimated to be in the range 8–11 kcal/mol. The results suggest that a slight change in the nature of the substituents on the phosphorus of the ligand can contribute considerably to the lability of the complex obtained. The NMR data are discussed and compared with those obtained for related phosphine chalcogenide systems.     

The Influence of Substituents at C2 Carbon Atom of Thiosemicarbazones {R(H)C2=N3‐N2(H)‐C1(=S)‐N1H2} on their Dentacy in PtII/PdII Complexes: Synthesis,Spectroscopy, and Crystal Structures

The coordination chemistry of platinum(II) with a series of thiosemicarbazones {R(H)C²=N³‐N²(H)‐C¹(=S)‐N¹H₂, R = 2‐hydroxyphenyl, H₂stsc; pyrrole, H₂ptsc; phenyl, Hbtsc} is described. Reactions of trans‐PtCl₂(PPh₃)₂ precursor with H₂stsc (or H₂ptsc) in 1 : 1 molar ratio in the presence of Et₃N base yielded complexes, [Pt(η³‐ O, N³, S‐stsc)(PPh₃)] ( 1 ) and [Pt(η³‐ N⁴, N³, S‐ptsc)(PPh₃)] ( 2 ), respectively. Further, trans‐PtCl₂(PPh₃)₂ and Hbtsc in 1 : 2 (M : L) molar ratio yielded a different compound, [Pt(η²‐ N³, S‐btsc)(η¹‐S‐btsc)(PPh₃)] ( 3 ). Complex 1 involved deprotonation of hydrazinic (‐N²H‐) and hydroxyl (‐OH) groups, and stsc^2? is coordinating via O, N³, S donor atoms, while complex 2 involved deprotonation of hydrazinic (‐N²H‐) and ‐N⁴H groups and ptsc^2? is probably coordinating via N⁴, N³, S donor atoms. Reaction of PdCl₂(PPh₃)₂ with Hbtsc‐Me {C₆H₅(CH₃)C²=N³‐N²(H)‐C¹(=S)‐N¹H₂} yielded a cyclometallated complex [Pd(η³‐C, N³, S‐btsc‐Me)(PPh₃)] ( 4 ). These complexes have been characterized with the help of analytical data, spectroscopic techniques {IR, NMR (¹H, ³¹P), U.V} and single crystal X‐ray crystallography ( 1 , 3 and 4 ). The effects of substituents at C² carbon of thiosemicarbazones on their dentacy and cyclometallation are emphasized.     

Ion Pairing and Salt Structure in Organic Salts through Diffusion,Overhauser, DFT and X‐ray Methods

Pulsed gradient spin‐echo (PGSE) diffusion characteristics for a) the new [brucinium][X] salts 6 a – f [ a : X=BF₄^?; b : X=PF₆^?; c : X=MeSO₃^?, d : X=CF₃SO₃^?; e : X=BArF^?; f : X=PtCl₃(C₂H₄)^?], b) 4‐tert‐butyl‐N‐benzyl analogue, 7 and c) the aryl carbocations (p‐R‐C₆H₄)₂CH 9 a (R=CH₃O) and 9 b (R=(CH₃)₂N), (p‐CH₃O‐C₆H₄)_xCPh_3?x⁺ 10 a – c (x=1–3, respectively) and (p‐R‐C₆H₄)₃C⁺ 11 (R=(CH₃)₂N) and 12 (R=H) all in several different solvents, are reported. The solvent dependence suggests strong ion pairing in CDCl₃, intermediate ion pairing in CD₂Cl₂ and little ion pairing in [D₆]acetone. ¹H, ¹⁹F HOESY NMR spectra (HOESY: heteronuclear Overhauser effect spectroscopy) for 6 and 7 reveal a specific approach of the anion with respect to the brucinium cation plus subtle changes, which are related to the anion itself. Further, for carbocations 9 – 12 , (all as BF₄^? salts) based on the NOE results, one finds marked changes in the relative positions of the BF₄^? anion. In these aryl cationic species the anion can be located either a) very close to the carbonium ion carbon b) in an intermediate position or c) proximate to the N or O atom of the p‐substituent and remote from the formally positive C atom. This represents the first example of such a positional dependence of an anion on the structure of the carbocation. DFT calculations support the experimental HOESY results. The solid‐state structures for 6 c and the novel Zeise's salt derivative, [brucinium][PtCl₃(C₂H₄)], 6 f , are reported. Analysis of ¹⁹⁵Pt NMR and other NMR measurements suggest that the η²‐C₂H₄ bonding to the platinum centre in 6 f is very similar to that found in K[PtCl₃(C₂H₄)]. Field dependent T₁ measurements on [brucinium][PtCl₃(C₂H₄)] and K[PtCl₃(C₂H₄)], are reported and suggested to be useful in recognizing aggregation effects.     

Crystal structure of K[PtCl3(caffeine)] and its interactions with important nitrogen-donor ligands

The crystal structure of K[PtCl₃(caffeine)] was determined. The coordination geometry around platinum is square-planar formed by N9 of the caffeine ligand and three Cl^? ions. The bond lengths and angles of K[PtCl₃(caffeine)] were compared with those reported for [PtCl₃(caffeine)]^? and K[PtCl₃(theobromine)]. At the level of the statistical significance of the data we have compared, no differences in the bond distances and angles for any of these compounds were noticed. Weak interactions between K⁺ and Cl^? are responsible for the formation of 1-D polymeric chains in the crystal structure of the complex. The interactions of K[PtCl₃(caffeine)] with inosine (Ino) and guanosine-5′-monophosphate (5′-GMP) were studied by ¹H NMR spectroscopy at 295 K in D₂O in a molar ratio of 1 : 1. The results indicate formation of the reaction product [PtCl₃(Nu)] (Nu=Ino or 5′-GMP) with the release of caffeine from the coordination sphere of the starting complex. The higher stability of the bond between the Pt(II) ion and Ino or 5′-GMP compared to the stability of the platinum–caffeine bond is confirmed by density functional theory calculations (B3LYP/LANL2DZp) using as models 9-methylhypoxanthine and 9-methylguanine.     

Synthese und Charakterisierung von Aquapentachloroplatinaten(IV) – Struktur von [K(18-Krone-6)][PtCl5(H2O)]

Synthesis and Characterization of Aquapentachloroplatinates(IV) – Structure of [K(18-crown-6)][PtCl₅(H₂O)] The crown ether complex of the aquapentachloroplatinic acid of the composition [H₁₃O₆][PtCl₅(H₄O₂)] · 2(18-cr-6) ( 2 ) reacts with K₂CO₃ and [NⁿBu₄]OH in aqueous solution to give [K(18-cr-6)][PtCl₅(H₂O)] ( 5 a ) and [NⁿBu₄][PtCl₅(H₂O)] · ¹/₂ (18-cr-6) · H₂O ( 5 b ), respectively. Both compounds were characterized by microanalysis, vibrational (IR, Raman) and NMR (¹H, ¹³C, ¹⁹⁵Pt) spectroscopy. The X-ray structure analysis of 5 a (orthorhombic, pnma; a = 16,550(4), b = 18,044(3), c = 7,415(1) Å; Z = 4; R1 = 0,0183; wR2 = 0,0414) reveals that the crystal is threaded by chains built up of [PtCl₅(H₂O)]^? and [K(18-cr-6)]⁺ units. There are tight K …? Cl contacts (d(K? Cl1)) = 3,0881(9) Å and O_W? H? O_cr hydrogen bridges (d(O1 …? O2) = 2,806(3) Å) between these units. The coordination polyhedron [PtCl₅O] has approximately C_4v symmetry.     

Cadmium(II) complexes with phosphine tellurides: synthesis and multinuclear (31P, 125Te,and 113Cd) NMR characterization in solution

New cadmium(II) complexes with phosphine telluride ligands of the type CdX₂(R₃PTe)_n [X?=?ClO₄^?, n?=?4: R?=?n-Bu (1), Me₂?N (2), C₅H₁₀?N (3), C₄H₈?N (4) or OC₄H₈?N (5); X?=?Cl^–, n?=?2: R?=?n-Bu (6), Me₂?N (7), C₅H₁₀?N (8), C₄H₈?N (9) or OC₄H₈?N (10)] have been synthesized and characterized by elemental analyses, IR and multinuclear (³¹P, ¹²⁵Te, and ¹¹³Cd) NMR spectroscopy. In particular, the solution structures of these complexes were confirmed by ¹¹³Cd NMR at low temperature, which displays a quintuplet for each of the perchlorate complexes and a triplet for each of the chloride complexes due to coupling with four and two equivalent phosphorus atoms, respectively, indicating a four-coordinate tetrahedral geometry for the metal center. These multiplet features were further accompanied by one bond Te–Cd couplings, clearly showing that the ligand is coordinated to the metal through tellurium. The results are discussed and compared with those obtained for closely related phosphine chalcogenide analogs.     

Accurate prediction of 195Pt-NMR chemical shifts for hydrolysis products of [PtCl6]2− in acidic and alkaline aqueous solutions by non-relativistic DFT computational protocols

The ¹⁹⁵Pt-NMR chemical shifts of all possible hydrolysis products of [PtCl₆]^2? in acidic and alkaline aqueous solutions are calculated employing simple non-relativistic density functional theory computational protocols. Particularly, the GIAO-PBE0/SARC-ZORA(Pt) ∪ 6-31 + G(d)(E) computational protocol augmented with the universal continuum solvation model (SMD) performs the best for calculation of the ¹⁹⁵Pt-NMR chemical shifts of the Pt(IV) complexes existing in acidic and alkaline aqueous solutions of [PtCl₆]^2?. Excellent linear plots of δ_calcd(¹⁹⁵Pt) chemical shifts versus δ_exptl(¹⁹⁵Pt) chemical shifts and δ_calcd(¹⁹⁵Pt) versus the natural atomic charge Q_Pt are obtained. Very small changes in the Pt–Cl and Pt–O bond distances of the octahedral [PtCl₆]^2?, [Pt(OH)₆]^2?, and [Pt(OH₂)₆]⁴⁺ complexes have significant influence on the computed σ^{iso 195}Pt magnetic shielding tensor elements of the anionic [PtCl₆]^2? and the computed δ ¹⁹⁵Pt chemical shifts of [Pt(OH)₆]^2? and [Pt(OH₂)₆]⁴⁺. An increase of the Pt–Cl and Pt–O bond distances by 0.001 Å (1 mÅ) is accompanied by a downfield shift increment of 17.0, 19.4, and 37.6 ppm mÅ^?1, respectively. Counter-anion effects in the case of the highly positive charged complexes drastically improve the accuracy of the calculated ¹⁹⁵Pt chemical shifts providing values very close to the experimental ones.     

cis-Di­chloro­bis­(triethyl­arsine)­platinum(II) and cis-di­chloro­bis­(triethyl­phosphine)­platinum(II)

The crystal structure of cis-[PtCl₂(C₆H₁₅As)₂], (I), is isostructural with a previously reported structure of cis-[PtCl₂(C₆H₁₅P)₂], (II). A new polymorph of (II) is also reported here. Selected geometrical parameters in the arsine complex are Pt—Cl 2.3412 (12) and 2.3498 (13), Pt—As 2.3563 (6) and 2.3630 (6) Å, Cl—Pt—Cl 88.74 (5), As—Pt—As 97.85 (2), and Cl—Pt—As 171.37 (4) and 177.45 (4)°. Corresponding parameters in the phosphine complex are Pt—Cl 2.364 (2) and 2.374 (2), Pt—P 2.264 (2) and 2.262 (2) Å, Cl—Pt—Cl 85.66 (9), P—Pt—P 98.39 (7), and Cl—Pt—P 170.26 (7) and 176.82 (8)°.     

Hydrogen‐bonded chains in three cis‐dichloridoplatinum(II) complexes bearing piperidine and amine ligands

The crystal structures of cis‐dichlorido(ethylamine‐κN)(piperidine‐κN)platinum(II), [PtCl₂(C₂H₇N)(C₅H₁₁N)], (I), cis‐dichlorido(3‐methoxyaniline‐κN)(piperidine‐κN)platinum(II), [PtCl₂(C₅H₁₁N)(C₇H₉NO)], (II), and cis‐dichlorido(piperidine‐κN)(quinoline‐κN)platinum(II), [PtCl₂(C₅H₁₁N)(C₉H₇N)], (III), have been determined at 100 K in order to verify the influence of the nonpiperidine ligand on the geometry and crystal packing. The crystal packing is characterized by N—H...Cl hydrogen bonding, resulting in the formation of chains of molecules connected in a head‐to‐tail fashion. Hydrogen‐bonding interactions play a major role in the packing of (I), where the chains further aggregate into planes, but less so in the case of (II) and (III), where π–π stacking interactions are of greater importance.     

A novel 8‐carboxyindeno[1,2‐b]quinoxalin‐11‐one thio­semi­carbazone zinc(II) Schiff base complex

In the novel title binuclear zinc(II) Schiff base complex, bis­(μ‐11‐thio­semicarbazonoindeno[1,2‐b]quinoxaline‐8‐carboxylato)bis­[(dimethyl sulfoxide)zinc(II)] dimethyl sulfoxide tri­solvate, [Zn₂(C₁₇H₉N₅O₂S)₂(C₂H₆OS)₂]·3C₂H₆OS, each Zn^II atom is five‐coordinated and situated in a distorted square‐pyramidal environment, coordinated by two L²⁻ ligands and one dimethyl sulfoxide mol­ecule. Each L²⁻ ligand, which coordinates to two Zn^II atoms, has two parts. One part, acting in a tridentate chelating mode, coordinates to one Zn^II atom through two N atoms and one S atom, while another part coordinates to another Zn^II atom through a monodentate carboxylate group. The whole complex has a dimeric structure. The coordination mode of the nearly planar L²⁻ ligand is quite different from the most common mode for Schiff bases.     

Reactivity of Aquadiethylenetriamineplatinum(II) Ion with Disulfide Moiety Cystine: A Kinetic and Mechanistic Approach

Abstract

Substitution reactions of the complex [Pt(dien)H₂O]²⁺ (where dien = diethylentriamine or 1,5-diamino-3-azapentane) with sulfur-containing L-cystine have been studied in a 1.0 × 10^?1 mol dm^?3 aqueous perchlorate medium at various temperatures (298–323 K) and 4.45 ≤ pH ≤ 2.15 using UV-vis spectroscopy. The products obtained have been characterized by their infrared and ¹H NMR datasets at various pH levels and temperatures. From infrared and ¹H NMR data, products have indicated that [Pt(dien)H₂O]²⁺ reacted with L-cystine forming a Pt–S bond at low pH. At high pH, a product complex through the Pt–N bond has been formed. All rate constants have been evaluated from nonlinear double exponential plots. The activation parameters ΔH^# and ΔS^# have been determined using the Eyring equation. The products, S_Ni, and reversible rate constants have been evaluated.

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GRAPHICAL ABSTRACT      

Tetrakis(thione)platinum(II) complexes: synthesis,spectroscopic characterization,crystal structures,and in vitro cytotoxicity

A new series of platinum(II) complexes based on thione ligands with general formula [Pt(thione)₄]X₂ (X^??=?Cl^?, NO₃^?) has been synthesized and characterized using CHNS elemental analysis, infrared, ¹H and ¹³C solution-state NMR as well as ¹³C and ¹⁵N solid-state NMR spectroscopy, and X-ray crystallography. The spectroscopic methods confirm the coordination of Pt(II) with thiocarbonyl groups via sulfur of the thione ligands. The X-ray structures showed a distorted square planar geometry for 1, [Pt(MeImt)₄]Cl₂ (MeImt = N-Methylimidazolidine-2-thione) while the hydrogen bonding interactions in 7, [Pt(iPrImt)₄](NO₃)₂·0.6(H₂O) induce a bent see-saw distortion relative to the ideal square planar geometry. The in vitro cytotoxicity studies showed that 2, [Pt(EtImt)₄]Cl₂ is generally the most effective, a two-fold better cytotoxic agent than cisplatin and carboplatin against MCF7 (human breast cancer).     

Platinum Indolylphosphine Fluorido and Polyfluorido Complexes: An Interplay between Cyclometallation,Fluoride Migration,and Hydrogen Bonding

The reaction of [PtCl₂(COD)] (COD=1,5-cyclooctadiene) with diisopropyl-2-(3-methyl)indolylphosphine (iPr₂P(C₉H₈N)) led to the formation of the platinum(ii ) chlorido complexes, cis-[PtCl₂{iPr₂P(C₉H₈N)}₂] ( 1 ) and trans-[PtCl₂{iPr₂P(C₉H₈N)}₂] ( 2 ). The cis-complex 1 reacted with NEt₃ yielding the complex cis-[PtCl{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}] ( 3 ) bearing a cyclometalated κ²-(P,N)-phosphine ligand, while the isomer 2 with a trans-configuration did not show any reactivity towards NEt₃. Treatment of 1 or 3 with (CH₃)₄NF (TMAF) resulted in the formation of the twofold cyclometalated complex cis-[Pt{κ²-(P,N)-iPr₂P(C₉H₇N)}₂] ( 4 ). The molecular structures of the complexes 1–4 were determined by single-crystal X-ray diffraction. The fluorido complex cis-[PtF{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}] ⋅ (HF)₄ ( 5 ⋅ (HF)₄) was formed when complex 4 was treated with different hydrogen fluoride sources. The Pt(ii ) fluorido complex 5 ⋅ (HF)₄ exhibits intramolecular hydrogen bonding in its outer coordination sphere between the fluorido ligand and the NH group of the 3-methylindolyl moiety. In contrast to its chlorido analogue 3 , complex 5 ⋅ (HF)₄ reacted with CO or the ynamide 1-(2-phenylethynyl)-2-pyrrolidinone to yield the complexes trans-[Pt(CO){κ²-(P,C)-iPr₂P(C₉H₇NCO)}{iPr₂P(C₉H₈N)}][F(HF)₄] ( 7 ) and a complex, which we suggest to be cis-[Pt{C=C(Ph)OCN(C₃H₆)}{κ²-(P,N)-iPr₂P(C₉H₇N)}{iPr₂P(C₉H₈N)}][F(HF)₄] ( 9 ), respectively. The structure of 9 was assigned on the basis of DFT calculations as well as NMR and IR data. Hydrogen bonding of HF and NH to fluoride was proven to be crucial for the existence of 7 and 9 .