cis-Bis(phosphine)platinum(II) complexes with pyrimidyl nucleobases. Synthesis, characterization, and crystal structures of cis-(1-methylthyminato-N3)(N,N-dimethylformamide-O)(1,1'-bis(diphenylphosphino)ferrocene)platinum(II) tetrafluoroborate-dichloromethane, [(dppf)Pt(1-MeTy(-H))(DMF)]BF4.cntdot.CH2Cl2, and cis-(1-methylthyminato-N3)(1-methylcytosine-N3)(1,1'-bis(diphenylphosphino)ferrocene)platinum(II) tetrafluoroborate, [(dppf)Pt(1-MeTy(-H))(1-MeCy)]BF4
Abstract:The dinuclear complex [(dppf)Pt(mu-OH)]2(BF4)2, where dppf is 1,1'-bis(diphenylphosphino)ferrocene, reacts with 1-methylthymine (1-MeTy), in dimethylformamide, dimethyl sulfoxide, or acetonitrile, to give the mononuclear complex [(dppf)Pt(1-MeTy(-H))(S)]+. The dimethylformamide adduct (S = DMF), [(dppf)Pt(1-MeTy(-H))(DMF)]BF4.CH2Cl2 (1), has been characterized by single-crystal X-ray analysis. The complex crystallizes in the orthorhombic system, space group P2(1)2(1)2(1), with a = 13.492 (3) angstrom, b = 14… Show more
“…In the isolated complex 1a the thyminate moiety acts as monodentate ligand leaving the fourth position around the metal centre available for the coordination of a solvent molecule. A similar binding mode of the thymine was early shown in the interaction with the hydroxo complex cis ‐[(dppf)Pt(μ‐OH)] 2 2+ [dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene] 9.…”
Section: Resultssupporting
confidence: 61%
“…In line with the presence of different types of donor atoms trans to the PMe 3 ligands, the 31 P NMR spectrum of the product shows well separated doublets ( 2 J PP = 25.6 Hz), at δ = −23.1 ( 1 J PPt = 3169 Hz) and −29.1 ( 1 J PPt = 3892 Hz). The deprotonation of the nucleobase is evidenced in the proton spectrum by the disappearance of the N(3)H resonance at δ = 11.2 and the concomitant shift to higher field of the H(6) resonance, which is observed as a 1:3:3:1 quadruplet ( 4 J HH ≈︁ 1 Hz) at δ = 7.40, slightly shielded with respect to the free base (δ = 7.49) 9.…”
1-Methylthymine (1-MeTy) reacts reversibly with the hydroxo complexes cis-[(PMe 3 ) 2 Pt(µ-OH)] 2 X 2 (X − = NO 3 ; ClO 4 ) in various solvents (S = CH 3 CN, H 2 O, DMSO) to give the thyminate derivatives cis-[(PMe 3 ) 2 Pt{1-MeTy(−H)}(S)]X that have been isolated as pure compounds when S is CH 3 CN. The single-crystal X-ray structure of cis-[(PMe 3 ) 2 Pt{1-MeTy(−H)}(CH 3 CN)]ClO 4 shows that the N(3)-platinated nucleobase acts as a monodentate ligand and a molecule of CH 3 CN completes the coordination sphere of the metal. Crystals of the acetamidine derivative cis-[(PMe 3 ) 2 Pt{1-MeTy(−H)}{CH 3 C(NH)NH 2 }]X were isolated from an acetonitrile solution of this complex, in the presence of small amounts of water, after several months at room temperature, [a]
“…In the isolated complex 1a the thyminate moiety acts as monodentate ligand leaving the fourth position around the metal centre available for the coordination of a solvent molecule. A similar binding mode of the thymine was early shown in the interaction with the hydroxo complex cis ‐[(dppf)Pt(μ‐OH)] 2 2+ [dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene] 9.…”
Section: Resultssupporting
confidence: 61%
“…In line with the presence of different types of donor atoms trans to the PMe 3 ligands, the 31 P NMR spectrum of the product shows well separated doublets ( 2 J PP = 25.6 Hz), at δ = −23.1 ( 1 J PPt = 3169 Hz) and −29.1 ( 1 J PPt = 3892 Hz). The deprotonation of the nucleobase is evidenced in the proton spectrum by the disappearance of the N(3)H resonance at δ = 11.2 and the concomitant shift to higher field of the H(6) resonance, which is observed as a 1:3:3:1 quadruplet ( 4 J HH ≈︁ 1 Hz) at δ = 7.40, slightly shielded with respect to the free base (δ = 7.49) 9.…”
1-Methylthymine (1-MeTy) reacts reversibly with the hydroxo complexes cis-[(PMe 3 ) 2 Pt(µ-OH)] 2 X 2 (X − = NO 3 ; ClO 4 ) in various solvents (S = CH 3 CN, H 2 O, DMSO) to give the thyminate derivatives cis-[(PMe 3 ) 2 Pt{1-MeTy(−H)}(S)]X that have been isolated as pure compounds when S is CH 3 CN. The single-crystal X-ray structure of cis-[(PMe 3 ) 2 Pt{1-MeTy(−H)}(CH 3 CN)]ClO 4 shows that the N(3)-platinated nucleobase acts as a monodentate ligand and a molecule of CH 3 CN completes the coordination sphere of the metal. Crystals of the acetamidine derivative cis-[(PMe 3 ) 2 Pt{1-MeTy(−H)}{CH 3 C(NH)NH 2 }]X were isolated from an acetonitrile solution of this complex, in the presence of small amounts of water, after several months at room temperature, [a]
“…Similarly, dppf was chosen because it is chelating and, among common chelating bis-phosphine ligands, has one of the widest bite angles. This angle has a major influence on the structure of the resulting complex and the corresponding catalytic properties. − For comparison, to evaluate the impact of dppf on the electronic and catalytic properties of the Fe II S 2 P 2 center, 2 , which features an N-containing bis-phosphine ligand (NP 2 ) instead of dppf, was synthesized. The ligand NP 2 is easily obtained by reaction of two equivalents of Ph 2 PCH 2 OH with glycine methyl ester in refluxing ethanol .…”
Abstract:Two pentacoordinate mononuclear iron carbonyls of the form (bdt)Fe(CO)P 2 [bdt = benzene-1,2-dithiolate; P 2 = 1,1'-diphenylphosphinoferrocene (1) or methyl-2-{bis(diphenylphosphinomethyl)amino}acetate (2)] were prepared as functional, biomimetic models for the distal iron (Fe d ) of the active site of [FeFe]-hydrogenase. Xray crystal structures of the complexes reveal that, despite similar ν(CO) stretching band frequencies, the two complexes have different coordination geometries. In X-ray crystal structures, the iron center of 1 is in a distorted trigonal bipyramidal arrangement, and that of 2 is in a distorted square pyramidal geometry. Electrochemical investigation shows that both complexes catalyze electrochemical proton reduction from acetic acid at mild overpotential, 0.17 and 0.38 V for 1 and 2, respectively. Although coordinatively unsaturated, the complexes display only weak, reversible binding affinity towards CO(1 bar). However, ligand centered protonation by the strong acid, HBF 4 .OEt 2 , triggers quantitative CO uptake by 1 to form a dicarbonyl analogue [1(H)-CO] + that can be reversibly converted back to 1 by deprotonation using NEt 3 . Both crystallographically determined distances within the bdt ligand and DFT calculations suggest that the iron centers in both 1 and 2 are partially reduced at the expense of partial oxidation of the bdt ligand. Ligand protonation interrupts this extensive electronic delocalization between the Fe and bdt making 1(H) + susceptible to external CO binding.3
“…Water-soluble tris(hydroxymethyl)phosphine (THP) was produced upon reaction of THPC with a suitable base (e.g., triethylamine or sodium bicarbonate buffer) (Scheme ) . The transition metal chemistry of THP and other functionalized phosphines, over the years, has enabled the development of a wide spectrum of water-soluble transition metal/organometallic compounds for potential use in biphasic catalysis , and biomedicine. , 1 …”
mentioning
confidence: 99%
“…The ease of transformation of P−H bonds into P−C bonds (as outlined in Scheme ) is, undoubtedly, a synthetic novelty and the (hydroxymethyl)phosphorus compounds have provided a diverse range of chemical, catalytic, biological, environmental, and biomedical applications. − Despite the potential academic interest and scope for further technological advances, formylation reactions of functionalized phosphorus hydrides and, especially, of multinuclear phosphorus hydrides (i.e., bis-, tris-, or tetraphosphines) have, surprisingly, remained largely unexplored.…”
Water is an environmentally (and biologically) benign solvent, and therefore, development of chemistry in aqueous media has long been a desirable goal for chemists. In particular, chemistry of water-soluble transition metal compounds has gained considerable prominence in recent years because of their usefulness in biphasic (aqueous-organic) catalysis 1 and biomedicine. 2 High solubility of transition metal compounds in water becomes a primary requirement in the design and development of catalysts for use under biphasic media because of the need for efficient separation and recovery of expensive transition metal catalysts (in aqueous media) from organic products. Additionally, the ability of specific transition metals to exert therapeutic (and diagnostic) influence on certain diseases has provided increased impetus in the development of new water-soluble and in vivo-stable transition metal compounds. 2,3 Of the various ligands available to stabilize specific oxidation states of transition metals and to produce aqueous soluble coordination compounds, functionalized phosphines are the most attractive class of ligands because of their versatile coordination chemistry. While aqueous soluble di-or trisulfonated arylphosphines, such as P(m-C 6 H 4 SO 3 Na) 3 , have largely been employed in the development of highly active water-soluble transition metal catalysts, 1 hydrophilic alkylphosphines are being highly sought after in order to gain specific structure-activity advantages in both catalytic and biomedical applications. In this context, the formylation of PH 3 , first reported by Hoffman et al., to produce tetrakis(hydroxymethyl)phosphonium chloride (THPC) has provided one of the earliest examples for the synthesis of hydrophilic alkylphosphines (Scheme 1). 4 Water-soluble tris(hydroxymethyl)phosphine (THP) was produced upon reaction of THPC with a suitable base (e.g., triethylamine or sodium bicarbonate buffer) (Scheme 1). 5 The transition metal chemistry of THP and other functionalized phosphines, over the years, has enabled the development of a wide spectrum of water-soluble transition metal/organometallic compounds for potential use in biphasic catalysis 5,6 and biomedicine. 7,8 The ease of transformation of P-H bonds into P-C bonds (as outlined in Scheme 1) is, undoubtedly, a synthetic novelty and the (hydroxymethyl)phosphorus compounds have provided a diverse range of chemical, catalytic, biological, environmental, and biomedical applications. 5-10 Despite the potential academic interest and scope for further technological advances, formylation reactions of functionalized phosphorus hydrides and, especially, of multinuclear phosphorus hydrides (i.e., bis-, tris-, or tetraphosphines) have, surprisingly, remained largely unexplored.It must be recognized that PH 3 , in its pure form, is an extremely hazardous chemical compound. It ignites in air at about 150°C and decomposes to produce phosphoric acid. 11 In its impure form, PH 3 gas is spontaneously inflammable at room temperature and this insta-
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