Disodium Tetrasupersilyltetragallanediide Na2Ga4R*4·2THF (R* = SitBu3) − Preparation of a Novel Gallium Cluster Compound via Dichlorodisupersilyldigallane R*2Ga2Cl2

Abstract

Red tetragallanediide Na 2 Ga 4 R* 4 •2THF was prepared by reduction of the monogallane R*GaCl 2 •THF in heptane or the tetrahedro-tetragallane R* 4 Ga 4 in benzene/tetrahydrofuran (THF) with sodium at 100 °C. Potassium worked analogously as a reduction agent. As an intermediate of the dehalogenation of R*GaCl 2 •THF, the orange digallane R* 2 Ga 2 Cl 2 and the dark violet tetrahedrane R* 4 Ga 4 were formed. The extreme air-and moisture-sensitive Na 2 Ga 4 R* 4 •2THF was stable against Me 3 SiCl, but reacted with oxygen under formation of R* 4 Ga 4 , and with GaBr under formation of sev-

Oxidative Addition of Group 13 and 14 Metal Halides and Alkyls to Ga(DDP) (DDP = Bulky Bisimidinate)

“…The Ga−Cl bond length of 2.1980(11) Å is shorter than those in [(DDP)GaCl 2 ] (2.228(1) Å and 2.218(1) Å) but well within the range for other Ga−Cl bond distances reported in literature. The Ga−Si bond length of 2.3860(13) Å is significantly shorter than that in the Ga(I) tetramer [{( t Bu 3 Si)Ga} 4 ] (2.45 Å) or the Ga(III) dihalide [( t Bu 3 Si)GaCl 2 (THF)] (2.42 Å) . Similar bond distances are reported for example for the dimeric compound [{(Me 3 Si) 3 SiGaMeCl} 2 ] …”

“…The Ga-Si bond length of 2.3860(13) Å is significantly shorter than that in the Ga(I) tetramer [{( t Bu 3 Si)Ga} 4 ] (2.45 Å) 52 or the Ga(III) dihalide [( t Bu 3 Si)GaCl 2 (THF)] (2.42 Å). 53 Similar bond distances are reported for example for the dimeric compound [{(Me 3 Si) 3 -SiGaMeCl} 2 ]. 54 Whereas no reaction of Ga(DDP) is observed in the presence of fluorobenzene or chlorobenzene, decomposition and undefined products are obtained with CH 2 Cl 2 and CHCl 3 .…”

Oxidative Addition of Group 13 and 14 Metal Halides and Alkyls to Ga(DDP) (DDP = Bulky Bisimidinate)

“…The Ga−Cl bond length of 2.1980(11) Å is shorter than those in [(DDP)GaCl 2 ] (2.228(1) Å and 2.218(1) Å) but well within the range for other Ga−Cl bond distances reported in literature. The Ga−Si bond length of 2.3860(13) Å is significantly shorter than that in the Ga(I) tetramer [{( t Bu 3 Si)Ga} 4 ] (2.45 Å) or the Ga(III) dihalide [( t Bu 3 Si)GaCl 2 (THF)] (2.42 Å) . Similar bond distances are reported for example for the dimeric compound [{(Me 3 Si) 3 SiGaMeCl} 2 ] …”

“…The Ga-Si bond length of 2.3860(13) Å is significantly shorter than that in the Ga(I) tetramer [{( t Bu 3 Si)Ga} 4 ] (2.45 Å) 52 or the Ga(III) dihalide [( t Bu 3 Si)GaCl 2 (THF)] (2.42 Å). 53 Similar bond distances are reported for example for the dimeric compound [{(Me 3 Si) 3 -SiGaMeCl} 2 ]. 54 Whereas no reaction of Ga(DDP) is observed in the presence of fluorobenzene or chlorobenzene, decomposition and undefined products are obtained with CH 2 Cl 2 and CHCl 3 .…”

Heats of Hydrogenation of Compounds Featuring Main Group Elements and with the Potential for Multiply Bonding

“…This shows that the alkali ion influences the chemistry of the species, and it suggests that they are involved in the bonding. Our results thus indicate that the compound should be described as a cluster compound, as has been done in the case of other compounds involving Group 13 elements and Na 29 …”

Bis[μ3-1,8-bis(triisopropylsilylamido)naphthalene]bis(tetrahydrofuran)di-μ3-oxido-dimanganese(III)disodium

“…These differences are presumably a consequence of the differing coordination environments in these two complexes. The Na1-O2 distance in (I) is significantly longer than the Na1-O1 distance, but it lies within the range of other Na-THF interactions in the literature (Allen, 2002) and is very similar to analogous Na-O distances in other complexes, such as [(THF) 3 Na]-[(N 2 )Mo{N(Ad)C 6 H 3 -2,6-Me 2 } 3 ] [2.254 (10) Å ; Peters et al, 1999] and Na 2 Ga 4 (Si t Bu 3 ) 4 Á2THF [2.252 (3) Å ; Wiberg et al, 2002]. The geometry around atom O1 is highly distorted trigonal pyramidal [Na1-O1-Mn1 i = 156.41 (14) ], with atom O1 lying 0.286 (2) Å out of the plane defined by atoms Mn1, Mn1 i and Na1.…”

Oxidative Addition of Group 13 and 14 Metal Halides and Alkyls to Ga(DDP) (DDP = Bulky Bisimidinate)

“…The Ga−Cl bond length of 2.1980(11) Å is shorter than those in [(DDP)GaCl 2 ] (2.228(1) Å and 2.218(1) Å) but well within the range for other Ga−Cl bond distances reported in literature. The Ga−Si bond length of 2.3860(13) Å is significantly shorter than that in the Ga(I) tetramer [{( t Bu 3 Si)Ga} 4 ] (2.45 Å) or the Ga(III) dihalide [( t Bu 3 Si)GaCl 2 (THF)] (2.42 Å) . Similar bond distances are reported for example for the dimeric compound [{(Me 3 Si) 3 SiGaMeCl} 2 ] …”

“…The Ga-Si bond length of 2.3860(13) Å is significantly shorter than that in the Ga(I) tetramer [{( t Bu 3 Si)Ga} 4 ] (2.45 Å) 52 or the Ga(III) dihalide [( t Bu 3 Si)GaCl 2 (THF)] (2.42 Å). 53 Similar bond distances are reported for example for the dimeric compound [{(Me 3 Si) 3 -SiGaMeCl} 2 ]. 54 Whereas no reaction of Ga(DDP) is observed in the presence of fluorobenzene or chlorobenzene, decomposition and undefined products are obtained with CH 2 Cl 2 and CHCl 3 .…”

Heats of Hydrogenation of Compounds Featuring Main Group Elements and with the Potential for Multiply Bonding

“…This shows that the alkali ion influences the chemistry of the species, and it suggests that they are involved in the bonding. Our results thus indicate that the compound should be described as a cluster compound, as has been done in the case of other compounds involving Group 13 elements and Na 29 …”

Bis[μ3-1,8-bis(triisopropylsilylamido)naphthalene]bis(tetrahydrofuran)di-μ3-oxido-dimanganese(III)disodium

“…These differences are presumably a consequence of the differing coordination environments in these two complexes. The Na1-O2 distance in (I) is significantly longer than the Na1-O1 distance, but it lies within the range of other Na-THF interactions in the literature (Allen, 2002) and is very similar to analogous Na-O distances in other complexes, such as [(THF) 3 Na]-[(N 2 )Mo{N(Ad)C 6 H 3 -2,6-Me 2 } 3 ] [2.254 (10) Å ; Peters et al, 1999] and Na 2 Ga 4 (Si t Bu 3 ) 4 Á2THF [2.252 (3) Å ; Wiberg et al, 2002]. The geometry around atom O1 is highly distorted trigonal pyramidal [Na1-O1-Mn1 i = 156.41 (14) ], with atom O1 lying 0.286 (2) Å out of the plane defined by atoms Mn1, Mn1 i and Na1.…”

Oxidative Addition of Group 13 and 14 Metal Halides and Alkyls to Ga(DDP) (DDP = Bulky Bisimidinate)

“…The Ga−Cl bond length of 2.1980(11) Å is shorter than those in [(DDP)GaCl 2 ] (2.228(1) Å and 2.218(1) Å) but well within the range for other Ga−Cl bond distances reported in literature. The Ga−Si bond length of 2.3860(13) Å is significantly shorter than that in the Ga(I) tetramer [{( t Bu 3 Si)Ga} 4 ] (2.45 Å) or the Ga(III) dihalide [( t Bu 3 Si)GaCl 2 (THF)] (2.42 Å) . Similar bond distances are reported for example for the dimeric compound [{(Me 3 Si) 3 SiGaMeCl} 2 ] …”

“…The Ga-Si bond length of 2.3860(13) Å is significantly shorter than that in the Ga(I) tetramer [{( t Bu 3 Si)Ga} 4 ] (2.45 Å) 52 or the Ga(III) dihalide [( t Bu 3 Si)GaCl 2 (THF)] (2.42 Å). 53 Similar bond distances are reported for example for the dimeric compound [{(Me 3 Si) 3 -SiGaMeCl} 2 ]. 54 Whereas no reaction of Ga(DDP) is observed in the presence of fluorobenzene or chlorobenzene, decomposition and undefined products are obtained with CH 2 Cl 2 and CHCl 3 .…”

Heats of Hydrogenation of Compounds Featuring Main Group Elements and with the Potential for Multiply Bonding

“…This shows that the alkali ion influences the chemistry of the species, and it suggests that they are involved in the bonding. Our results thus indicate that the compound should be described as a cluster compound, as has been done in the case of other compounds involving Group 13 elements and Na 29 …”

Bis[μ3-1,8-bis(triisopropylsilylamido)naphthalene]bis(tetrahydrofuran)di-μ3-oxido-dimanganese(III)disodium

“…These differences are presumably a consequence of the differing coordination environments in these two complexes. The Na1-O2 distance in (I) is significantly longer than the Na1-O1 distance, but it lies within the range of other Na-THF interactions in the literature (Allen, 2002) and is very similar to analogous Na-O distances in other complexes, such as [(THF) 3 Na]-[(N 2 )Mo{N(Ad)C 6 H 3 -2,6-Me 2 } 3 ] [2.254 (10) Å ; Peters et al, 1999] and Na 2 Ga 4 (Si t Bu 3 ) 4 Á2THF [2.252 (3) Å ; Wiberg et al, 2002]. The geometry around atom O1 is highly distorted trigonal pyramidal [Na1-O1-Mn1 i = 156.41 (14) ], with atom O1 lying 0.286 (2) Å out of the plane defined by atoms Mn1, Mn1 i and Na1.…”