Synthesis of amidate-hanging platinum mononuclear complexes by base hydrolysis of nitrile complexes

Uemura, Kazuhiro; Yamasaki, Kana; Fukui, Kôichi; Matsumoto, Kazuko

doi:10.1016/j.ica.2006.12.036

Cited by 8 publications

(3 citation statements)

References 21 publications

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“…The amidate-hanging Pt mononuclear complex, [Pt(piam) 2 (NH 3 ) 2 ]·2H 2 O, is a useful precursor for heterometal multinuclear complexes , because noncoordinated O atoms are easily bound to second metals in solution. Simply mixing [Pt(piam) 2 (NH 3 ) 2 ]·2H 2 O, CoCl 2 ·6H 2 O, and NaPF 6 in H 2 O afforded violet microcrystalline [Pt 2 Co(NH 3 ) 4 (piam) 4 ](PF 6 ) 2 ( 2 ).…”

Section: Resultsmentioning

confidence: 99%

Paramagnetic One-Dimensional Chain Complex Consisting of Three Kinds of Metallic Species Showing Magnetic Interaction through Metal–Metal Bonds

Uemura

Miyake

2019

Inorg. Chem.

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A heterometallic and paramagnetic one-dimensional (1-D) chain (3) aligned as −Rh(+2)−Rh(+2)− Pt(+2)−Co(+2)−Pt(+2)− with direct metal−metal bonds was obtained by HOMO−LUMO interactions at the σ* (d z 2 ) orbital between two kinds of complexes. The 1-D chains in 3 have relatively straight backbones because the raw material complexes, [Rh 2 (O 2 CCH 3 ) 4 ] and [Pt 2 Co(piam) 4 (NH 3 ) 4 ], are connected and stacked in a face-to-face fashion, where Co---Co are separated by about 13.3 Å with four different metals.Physical measurements revealed that 3 has a band gap between the σ-type conduction and valence bands, where dorbitals of the Co ion with three unpaired electrons are laid among them. The magnetic behavior of 3 was investigated and found to be consistent with a complex interaction involving both zero-field splitting and Pauli paramagnetism attributed to band formation superimposed on relatively strong exchange coupling (zJ = −22.2 cm −1 ) between two high-spin Co(+2) ions separated by the diamagnetic Pt−Rh−Rh−Pt.

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Section: Resultsmentioning

confidence: 99%

Paramagnetic One-Dimensional Chain Complex Consisting of Three Kinds of Metallic Species Showing Magnetic Interaction through Metal–Metal Bonds

Uemura

Miyake

2019

Inorg. Chem.

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“…To rationally introduce alkyl moieties at amines coordinated to Pt atoms in the 1D heterometallic complexes, amidate-hanging platinum mononuclear complexes cis -[Pt(piam) 2 (NH 2 CH 3 ) 2 ]·H 2 O, cis -[Pt(piam) 2 (NH 2 C 2 H 5 ) 2 ]·H 2 O, cis -[Pt(piam) 2 (NH 2 C 3 H 7 ) 2 ]·H 2 O, and cis -[Pt(piam) 2 (NH 2 C 4 H 9 ) 2 ] were used. These complexes were easily dimerized with aqua Pt complexes having corresponding alkyl amines, cis -[Pt(OH 2 ) 2 (NH 2 R) 2 ] (R = CH 3 , C 2 H 5 , C 3 H 7 and C 4 H 9 ), to provide dinuclear platinum complexes, [Pt 2 (piam) 2 (NH 2 R) 4 ]X 2 (X = anion).…”

Section: Resultsmentioning

confidence: 99%

“…Rhodium(III) chloride trihydrate and potassium tetrachloroplatinate(II) were obtained from Tanaka Kikinzoku Co. 40% NH 2 CH 3 aqua solution, 70% NH 2 C 2 H 5 aqua solution, NH 2 C 4 H 9 , NaClO 4 , and KI were obtained from Nacalai Tesque Co. NaPF 6 , pivalonitrile, and NH 2 C 3 H 7 were obtained from Tokyo Chemical Industry Co. AgNO 3 and AgPF 6 were obtained from Wako Co. cis -[PtI 2 (NH 2 CH 3 ) 2 ], cis -[PtI 2 (NH 2 C 2 H 5 ) 2 ], cis -[PtI 2 (NH 2 C 3 H 7 ) 2 ], and cis -[PtI 2 (NH 2 C 4 H 9 ) 2 ] were synthesized by a modified version of Dhara’s method. , cis -[Pt(piam) 2 (NH 2 CH 3 ) 2 ]·H 2 O, cis -[Pt(piam) 2 (NH 2 C 2 H 5 ) 2 ]·H 2 O, cis -[Pt(piam) 2 (NH 2 C 3 H 7 ) 2 ]·H 2 O, cis -[Pt(piam) 2 (NH 2 C 4 H 9 ) 2 ], [Rh 2 (O 2 CCH 3 ) 4 ], [{Rh 2 (O 2 CCH 3 ) 4 }{Pt 2 (piam) 2 (NH 3 ) 4 } 2 ] n (PF 6 ) 4 n ·6 n H 2 O ( 1 ), and [{Rh 2 (O 2 CCH 3 ) 4 }{Pt 2 (piam) 2 (NH 2 CH 3 ) 4 } 2 ](PF 6 ) 4 ( 2 ) were synthesized according to the previous procedures.…”

Section: Methodsmentioning

confidence: 99%

Improving the Solubility of Hexanuclear Heterometallic Extended Metal Atom Chain Compounds in Nonpolar Solvents by Introducing Alkyl Amine Moieties

2021

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The highest occupied molecular orbital−lowest unoccupied molecular orbital (HOMO−LUMO) interaction at the d z 2 orbital between two kinds of metal complex is useful for obtaining heterometallic one-dimensional (1D) chains as well as heterometallic metal string compounds (HMSCs). Platinum dinuclear complexes, [Pt 2 (piam) ray analyses revealed that 2−5 are hexanuclear complexes that are onedimensionally aligned as Pt−Pt−Rh−Rh−Pt−Pt with metal− metal bonds, where the alkyl moieties at end Pt atoms obstruct further 1D extension. Complexes 2−5 appear as if they are cut off from an infinite chain [{Rh 2 (O 2 CCH 3 ) 4 }-{Pt 2 (piam) 2 (NH 3 ) 4 } 2 ] n (PF 6 ) 4n •6nH 2 O (1) aligned as −{Pt−Pt−Rh−Rh−Pt−Pt} n −. The diffuse reflectance spectrum of 1 depicts broad shoulder bands, which are not present in the spectra of 2−5, proving that the infinite chain 1 forms a band structure.Compounds 4 and 5 with propyl or butyl moieties at amine ligands, respectively, are soluble in nonpolar solvents, such as CH 2 Cl 2 , without the dissociation of their hexanuclear structures. Taking advantage of their solubility, measurement of cyclic voltammetry in CH 2 Cl 2 become possible, which shows the quasi-reversible oxidation and reduction waves at 4: E ox = 0.86 V and E red = 0.69 V and 5: E ox = 0.87 V and E red = 0.53 V.

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Evidence of electronic interactions between end platinum atoms of hexanuclear units in heterometallic one-dimensional chains

Uemura

Sugiyama

2022

Journal of Molecular Structure

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Synthesis of amidate-hanging platinum mononuclear complexes by base hydrolysis of nitrile complexes

Cited by 8 publications

References 21 publications

Paramagnetic One-Dimensional Chain Complex Consisting of Three Kinds of Metallic Species Showing Magnetic Interaction through Metal–Metal Bonds

Paramagnetic One-Dimensional Chain Complex Consisting of Three Kinds of Metallic Species Showing Magnetic Interaction through Metal–Metal Bonds

Improving the Solubility of Hexanuclear Heterometallic Extended Metal Atom Chain Compounds in Nonpolar Solvents by Introducing Alkyl Amine Moieties

Evidence of electronic interactions between end platinum atoms of hexanuclear units in heterometallic one-dimensional chains

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