Metalation of 2,6-lutidine-functionalized bis(phosphoranimines) (Me3SiNPPr
i
2CH2)2C5H3N-2,6 (2) using MgBu2 in THF yielded the magnesium compound [Mg{(Me3SiNPPr
i
2CH)2C5H3N-2,6}THF] (3). Further reaction of 3 with 1 equiv of SnCl2 afforded the tin(II)
compound [{2-{Sn{C(Pr
i
2PNSiMe3)}}-6-{Sn{CH(Pr
i
2PNSiMe3)}Cl}}C5H3N]2 (4). Treatment of 2 with 2 equiv of Pb{N(SiMe3)2}2 afforded the lead(II) compound [{2-{Pb{C(Pr
i
2PNSiMe3)}}-6-{Pb{CH(Pr
i
2PNSiMe3)}N(SiMe3)2}}C5H3N]2 (5). X-ray structural analysis
revealed that 4 and 5 consist of a 1,3-dimetallacyclobutane and two metal(II) alkyl moieties.
Similar reaction of 3 with 1 equiv of GeCl2(dioxane), however, yielded the germanium(II)
compound
(6) without forming a similar 1,3-digermacyclobutane ring.
The dilithium compound [Li2{{N(SiMe3)C(Bu
t
)C(H)}2C4H2N2-2,3}(THF)2]2 (2) has been
obtained by dilithiation of 2,3-bis(trimethylsilylmethyl)pyrazine, (CH2SiMe3)2C4H2N2-2,3 (1),
using Bu
n
Li followed by the reaction with Bu
t
CN. Compounds of the heavier congeners
[Na2{{N(SiMe3)C(Bu
t
)C(H)}2C4H2N2-2,3}(THF)2]2 (3) and [K2{{N(SiMe3)C(Bu
t
)C(H)}2C4H2N2-2,3}(THF)3]2 (4) have been obtained by treating 2 with Bu
t
ONa or Bu
t
OK, respectively.
Treatment of 2 with 4 equiv of MgBr2(Et2O) yielded the binuclear magnesium complex [Mg2{{N(SiMe3)C(Bu
t
)C(H)}2C4H2N2-2,3}Br2(THF)4] (5). Similar metathesis reaction of 2 with 4
equiv of ZnCl2 gave the zwitterionic lithium zincate complex [Zn2{{N(SiMe3)C(Bu
t
)C(H)}2C4H2N2-2,3}Cl2(μ-Cl)2Li2(THF)6] (6). However, the reaction of 2 with 4 equiv of CdCl2
afforded a heterocyclic compound,
(7). X-ray structures
of compounds 2−7 have been determined.
This article is updated to cover the literature in the area of inorganic chemistry of alkali metals since 1993. The advancement in instrumentation and spectroscopic techniques in the past decade has provided the researchers with more powerful tools for structure determination of compounds. In this respect, alkalides containing mixed‐sandwich complexes of alkali metal cations, complexes with dimers or chains of alkali metal anions, electrides with alkali metal ions intercalating in zeolite, and interstitial hydride enclosed by an unusual (Li
+
)
8
cubic cage have been found or studied by NMR. With the successful preparation of Na
3
N recently, its correct structure has been revealed. The exact composition of ‘NaB
6
’ has also been determined. The role of alkali metals in trielide clusters of traditional Zintl polyanions has been demonstrated. Trimetallic Li‐Na‐K amides, alkoxide compounds, and highly aggregated cage structures of lithium‐heavier alkali metal alkoxides have been reported.
This article is updated to cover the literature in the area of inorganic chemistry of alkali metals since 1993. The advancement in instrumentation and spectroscopic techniques in the past decade has provided the researchers with more powerful tools for structure determination of compounds. In this respect, alkalides containing mixed‐sandwich complexes of alkali metal cations, complexes with dimers or chains of alkali metal anions, electrides with alkali metal ions intercalating in zeolite, and interstitial hydride enclosed by an unusual (Li
+
)
8
cubic cage have been found or studied by NMR. With the successful preparation of Na
3
N recently, its correct structure has been revealed. The exact composition of ‘NaB
6
’ has also been determined. The role of alkali metals in trielide clusters of traditional Zintl polyanions has been demonstrated. Trimetallic Li‐Na‐K amides, alkoxide compounds, and highly aggregated cage structures of lithium‐heavier alkali metal alkoxides have been reported.
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