Unexpected synthesis and structural characterization of Pt(II)Cl2-1,5-hexadiene from reaction of allyl chloride and K2PtCl4

Nair, Reji N.; Golen, James A.; Rheingold, Arnold L.; Grotjahn, Douglas B.

doi:10.1016/j.ica.2010.09.006

Cited by 5 publications

(7 citation statements)

References 9 publications

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“…The synthesis of the (9-oxabispidine)platinum complexes largely followed that of the parent bispidine complexes A1 – A3 . Thus, (1,5-hexadiene)platinum dichloride was reacted with 1 equiv of C in DMF at 65 °C to afford a yellow precipitate of {OC 6 H 10 (NH) 2 }PtCl 2 ( C1 ; Scheme ). The isolated C1 was then further reacted with Ag 2 (cbdca) in water to obtain, after removal of AgCl, an aqueous solution of {OC 6 H 10 (NH) 2 }Pt{(O 2 C) 2 C 4 H 6 }·5H 2 O ( C2 ), which was isolated after concentration.…”

Section: Results and Discussionmentioning

confidence: 99%

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Synthesis and Structures of 9-Oxabispidine Analogues of Cisplatin, Carboplatin, and Oxaliplatin

2016

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The literature synthesis of 9-oxabispidine [OC6H10(NH)2, C] has been revisited and optimized, which includes determination of the crystal structures of C, the secondary component trans-(PhSO2)NC4H6O(CH2I)2 (trans-III), and the unexpected solute intermediate OC6H10(NSO2Ph)2·(1)/2py (V·(1)/2py). The reaction of (1,5-hexadiene)platinum dichloride with C yields {OC6H10(NH)2}PtCl2 (C1), which is converted to {OC6H10(NH)2}Pt(cbdca)·5H2O (C2) and {OC6H10(NH)2}Pt(C2O4) (C3). In the crystal, C1 forms a planar 2D network by N-H··Cl and N-H··O hydrogen bonding. In the crystal structure of C2, which is isomorphous to the parent bispidine compound (A2), all complex molecules are encapsulated by a water shell. While complexes C1 and C3 are virtually insoluble in water, C2 dissolves quite well. The low cytotoxicity of compounds C1-C3 is explained by an increased polarity of the bonds in the C skeleton as a consequence of the electronegative O atom.

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Section: Results and Discussionmentioning

confidence: 99%

“…The reactions were performed with Schlenk-type glassware under argon. (1,5-Hexadiene)platinum dichloride was prepared according to the literature. A revised protocol for the synthesis of 9-oxabispidine ( C , C 6 H 12 N 2 O, fw 128.2) is included in the SI.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Structures of 9-Oxabispidine Analogues of Cisplatin, Carboplatin, and Oxaliplatin

2016

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“…Heating (1,5-hexadiene)PtCl 2 and 12 in DMF to 100 °C for 2 h gave the spiro[bispidin-dioxolane]–PtCl 2 complex 13 as a light yellow precipitate in almost quantitative yield (Scheme ). In the EI mass spectrum of 13 at an evaporation temperature of 350 °C, the molecular ion m / e = 449 (3%) was observed, which fragments by two successive HCl eliminations.…”

Section: Resultsmentioning

confidence: 99%

“…The reactions were performed under argon with Schlenk-type glassware. (C 6 H 10 )PtCl 2 , K 2 (cbdca), , and Ag 2 (cbdca) , were prepared as described. MS data refer to 195 Pt and 35 Cl isotopes.…”

Section: Methodsmentioning

confidence: 99%

Bispidin-9,9-diol Analogues of Cisplatin, Carboplatin, and Oxaliplatin: Synthesis, Structures, and Cytotoxicity

et al. 2016

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3,7-Diallyl-bispidin-9-one (6) (bispidin-9-one = 3,7-diazabicyclo[3.3.1]nonan-9-one) is converted to N-unsubstituted spiro[bispidin-9,2'-[1,3]dioxolane] (12; 35%). The ketal crystallizes in the forms of anhydrous 12a and the dihydrate 12b. The molecules in anhydrous 12a are linked to each other, forming N1-H1···N2-H2···N1* hydrogen-bond chiral helices of alternating chirality. In the dihydrate 12b, the ketal molecules are connected to a central string of water molecules by O3-H···O1 and O4-H···N1 hydrogen bonds, but not to themselves. Reaction of 12 with (1,5-hexadiene)PtCl2 affords almost quantitatively spiro[bispidin-9,2'-[1,3]dioxolane]PtCl2 (13). Cleavage of the ketal to retrieve the ketone produces the geminal diol (bispidin-9,9-diol)PtCl2 (14; 85%). Compound 14 reacts with Ag2cbdca (cbdca = 1,1-cyclobutanedicarboxylate) to give the dihydrate (bispidin-9,9-diol)Pt(cbdca)·2H2O (15b), which can be dehydrated to obtain anhydrous (bispidin-9,9-diol)Pt(cbdca) (15a). Similarly, anhydrous (bispidin-9,9-diol)Pt(oxalate) (16) is obtained. Crystal structures of 14 and 15b reveal association by various forms of O-H···O, O-H···Cl, N-H···Cl, and N-H···O hydrogen bonds. Biological studies showed a moderate cytotoxic activity of the bispidin-9,9-diol complexes 14-16, compared to the 9,9-unsubstituted bispidine complexes. No unspecific cytotoxicity of 14-16 up to 316 μM was found against the noncancer cell line HEK293.

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“…Previously, (1,5-hexadiene)PtCl 2 was reported to react with various 1,5-diphenylbispidin-9-ones in refluxing CHCl 3 to afford the corresponding (bispidin-9-one)PtCl 2 complexes . More recently, (MeCN) 2 PtCl 2 was reacted with (−)-sparteine in CH 2 Cl 2 to give ((−)-sparteine)PtCl 2 in low yield .…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Coordination Chemistry ofN,N-Diallylbispidine

2011

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The synthesis of 3,7-diallyl-3,7-diazabicyclo-[3.3.1]nonane (C 7 H 12 N 2 allyl 2 , 3) has been revisited, and several hitherto undetected byproducts have been identified. Pure 3 and these byproducts were isolated by both prep-GC and column chromatography. Monoprotonated 3 in the form of the PF 6 salt [(C 7 H 13 N 2 allyl 2 ]PF 6 (9) and the addition complexes of 3 to Ni(acac) 2 and CuI, (C 7 H 12 N 2 allyl 2 )Ni-(acac) 2 (10) and {(C 7 H 12 N 2 allyl 2 )Cu(μ-I)} 2 (11), have been prepared. From the reactions of {(η 3 -C 3 H 5 )M(μ-X)} 2 (M = Ni, Pd, Pt; X = Cl, Br) with 3 and TlPF 6 the complexes [(C 7 H 12 N 2 allyl 2 )M(η 3 -C 3 H 5 )]PF 6 (M = Ni (12a), Pd (12b), Pt (12c)) were obtained. Compounds 9−11 and 12b were characterized by X-ray crystallography. The reaction of (1,5-hexadiene)PtCl 2 with 3 gave, after HCl elimination, monomeric {C 7 H 12 N 2 (C 3 H 5 )CHCHCH 2 }PtCl (13a), and the presence of MeOH afforded {C 7 H 12 N 2 (C 3 H 5 )CH 2 CH(OMe)CH 2 }PtCl (13b), both compounds featuring novel anionic tridentate ligands. Furthermore, chiral N,N′-bis((R)-1-phenylethyl)-1,7octadiene-(S,S)-4,5-diamine (15) reacts with CuI to give [{(C 3 H 5 ) 2 C 2 H 4 N 2 (CHMePh) 2 }Cu(μ-I)] 2 ( 16). The unbound N-allyl functions on the ligands in the product complexes allow for immobilization of the transition metal complexes on polyester fibers.

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Unexpected synthesis and structural characterization of Pt(II)Cl2-1,5-hexadiene from reaction of allyl chloride and K2PtCl4

Cited by 5 publications

References 9 publications

Synthesis and Structures of 9-Oxabispidine Analogues of Cisplatin, Carboplatin, and Oxaliplatin

Synthesis and Structures of 9-Oxabispidine Analogues of Cisplatin, Carboplatin, and Oxaliplatin

Bispidin-9,9-diol Analogues of Cisplatin, Carboplatin, and Oxaliplatin: Synthesis, Structures, and Cytotoxicity

Synthesis and Coordination Chemistry ofN,N-Diallylbispidine

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