Reactivity of 5-Methylpyridyl-2-Selenolate With Platinoid Metal Precursors: Isolation of Tri and Hexanuclear Complexes via Se-Se and Se-C Bond Cleavage

• Published in: Journal of cluster science Vol. 35; no. 5; pp. 1549 - 1560
• Main Authors: Lokhande, Saili Vikram, Kulkarni, Atharva Yeshwant, Siddiki, Afsar Ali, Butcher, Raymond J., Chauhan, Rohit Singh
• Format: Journal Article
• Language: English
• Published: New York Springer US 01-06-2024; Springer Nature B.V
• Subjects: Catalysis; Chemistry; Chemistry and Materials Science; Cleavage; Inorganic Chemistry; Ligands; Molecular structure; Nanochemistry; NMR spectroscopy; Original Paper; Palladium; Phosphines; Physical Chemistry; Platinum; Single crystals; Substitution reactions; Palladium; NMR and Single crystal X-ray; Platinum; Selenolates
• ISSN: 1040-7278; 1572-8862
• DOI: 10.1007/s10876-024-02606-z

A series of palladium (II) and platinum (II) selenolate complexes have been isolated depending upon the nature of the phosphine ligand. The substitution reaction of [PdCl
2
(PPh
3
)
2
] with two equivalents of NaSeC
5
H
3
(5-Me)N resulted in the hexanuclear complex [Pd
6
Br
0.87
Cl
1.13
{2-SeC
5
H
3
(5-Me)N
2
}
2
(PPh
3
)
6
] (
1a
) whereas a chelated compound [Pt{κ-Se, κ-N: SeC
5
H
3
(5-Me)N}{SeC
5
H
3
(5-Me)N}(PPh
3
)] (
1b
) has been obtained in the case of [PtCl
2
(PPh
3
)
2
]. However, chelated phosphine as an ancillary ligand with a similar reaction by using [PtCl
2
(P∩P)] (P∩P = dppm, dppe) yielded
cis
-configured monomer [Pt{2-SeC
5
H
3
(5-Me)N}
2
(P∩P)]. The trinuclear complexes [M
3
(µ-Se)
3
(dppp)
3
]
2+
[M = Pd (
2d
), Pt (
2e
)] were isolated by reactions of [MCl
2
(dppp)] (M = Pd, Pt) with NaSeC
5
H
3
(5-Me)N via facile cleavage of Se-C bond in presence of chlorinated solvents. All the synthesized complexes have been characterized by elemental analyses,
1
H,
31
P{
1
H},
77
Se{
1
H} NMR spectroscopy. The molecular structure of complexes [Pd
6
Br
0.87
Cl
1.13
{2-SeC
5
H
3
(5-Me)}
2
(PPh
3
)
6
] (
1a
) and [Pt{2-SeC
5
H
3
(5-Me)N}
2
(dppm)].C
6
H
5
CH
3
(
2a
) were determined by single crystal X-ray diffraction analyses.