title: Thiourea monoanion and dianion complexes of rhodium(III) and ruthenium(II)

authors: Henderson, William

subjects: Crystal structures

abstract: The versatility of deprotonated thioureas as ligands is shown by the synthesis and characterisation of a range of rhodium(III) complexes of substituted thioureas, with support from a ruthenium(II) analogue in one case. Reaction of the complexes [LMCl(μ-Cl)]2 [M=Rh, L=η5-C5Me5 (Cp*); M=Ru, L=η6-p-cymene] with Na[MeNHC(S)NCN] and excess trimethylamine base gives the dinuclear complexes [LM{SC(=NCN)NMe}]2 containing chelate-bridging thiourea dianion ligands. The Ru complex was characterised by an X-ray diffraction study. The mononuclear complexes [Cp*Rh{SC(=NCN)NMe}(PPh3)] and [Cp*Rh{SC(=NPh)NPh}(PPh3)], containing chelating thiourea dianion ligands, were prepared by analogous reactions in the presence of triphenylphosphine. Reaction of [Cp*Rh{SC(=NCN)NMe}(PPh3)] with HCl, or [Cp*RhCl(μ-Cl)]2 with 2 equiv. of PPh3 and Na[MeNHC(S)NCN] (with no added base) gave the complex [Cp*RhCl{SC(=NCN)NHMe}(PPh3)], containing a (monodentate) S-bonded thiourea monoanion ligand, which was characterised by an X-ray diffraction study. The AsPh3 and SbPh3 analogues of this complex were also prepared and characterised. Reaction of [Cp*RhCl(μ-Cl)]2 with 2 equiv. of PPh3 or SbPh3 and PhNHC(S)NHPh or various trisubstituted thioureas PhNHC(S)NR1R2, triethylamine and NaBPh4 gave a range of cationic complexes [Cp*Rh{SC(=NR1R2)NPh}(EPh3)]+ (E=P, Sb), as their tetraphenylborate salts, in which the thiourea is bonded as a monoanion through the S and the NPh group. The corresponding reaction utilising 1,6-bis(diphenylphosphino)hexane (dpph) gave the dinuclear complex [Cp*Rh{SC(=N(CH2CH2)2O)NPh}]2(μ-η2-dpph) (BPh4)2.

text: Thiourea monoanion and dianion complexes of rhodium(III) and ruthenium(II) The versatility of deprotonated thioureas as ligands is shown by the synthesis and characterisation of a range of rhodium(III) complexes of substituted thioureas, with support from a ruthenium(II) analogue in one case. Reaction of the complexes [LMCl(μ-Cl)]2 [M=Rh, L=η5-C5Me5 (Cp*); M=Ru, L=η6-p-cymene] with Na[MeNHC(S)NCN] and excess trimethylamine base gives the dinuclear complexes [LM{SC(=NCN)NMe}]2 containing chelate-bridging thiourea dianion ligands. The Ru complex was characterised by an X-ray diffraction study. The mononuclear complexes [Cp*Rh{SC(=NCN)NMe}(PPh3)] and [Cp*Rh{SC(=NPh)NPh}(PPh3)], containing chelating thiourea dianion ligands, were prepared by analogous reactions in the presence of triphenylphosphine. Reaction of [Cp*Rh{SC(=NCN)NMe}(PPh3)] with HCl, or [Cp*RhCl(μ-Cl)]2 with 2 equiv. of PPh3 and Na[MeNHC(S)NCN] (with no added base) gave the complex [Cp*RhCl{SC(=NCN)NHMe}(PPh3)], containing a (monodentate) S-bonded thiourea monoanion ligand, which was characterised by an X-ray diffraction study. The AsPh3 and SbPh3 analogues of this complex were also prepared and characterised. Reaction of [Cp*RhCl(μ-Cl)]2 with 2 equiv. of PPh3 or SbPh3 and PhNHC(S)NHPh or various trisubstituted thioureas PhNHC(S)NR1R2, triethylamine and NaBPh4 gave a range of cationic complexes [Cp*Rh{SC(=NR1R2)NPh}(EPh3)]+ (E=P, Sb), as their tetraphenylborate salts, in which the thiourea is bonded as a monoanion through the S and the NPh group. The corresponding reaction utilising 1,6-bis(diphenylphosphino)hexane (dpph) gave the dinuclear complex [Cp*Rh{SC(=N(CH2CH2)2O)NPh}]2(μ-η2-dpph) (BPh4)2.

year: 2002-10-01

title: The complexity of absenteeism and turnover intention: Direct, mediation and moderation effects

authors: Vogelzang, Ciska (Francisca Monica)

subjects: absenteeism

abstract: Absenteeism and turnover in the workplace are complex phenomena that have implications for organisations and individuals alike. This study investigated the relationships of attitudinal factors with absenteeism and turnover intentions at a large healthcare organisation in the Bay of Plenty. A questionnaire completed by 407 employees had several measures such as job involvement, job satisfaction, organisational commitment (affective and continuance commitment), perceived organisational support, perceived supervisor support, work-to-family conflict, family-to-work conflict, team cohesion, regional identification and turnover intention. Absenteeism data were collected from personnel records.
The results indicated a probable association of job satisfaction, work-to-family conflict and perceived supervisor support with absenteeism, while turnover intention was associated with all predictors except continuance commitment. Perceived organisational support partially mediated the relationship between perceived supervisor support and turnover intention. No moderator effects were found for job involvement, perceived supervisor support and team cohesion on relationships between work-to-family conflict and affective commitment/job satisfaction and perceived organisational support and affective commitment respectively, however strong main effects were shown for job involvement and team cohesion.
The main finding is that organisations must understand how organisational and supervisor support increases job satisfaction and affective commitment and decreases work-to-family conflict, which lowers absenteeism and turnover intention. The detection of high levels of regional identification indicate the need to acknowledge this construct, particularly in relation to turnover intention.

text: The complexity of absenteeism and turnover intention: Direct, mediation and moderation effects Absenteeism and turnover in the workplace are complex phenomena that have implications for organisations and individuals alike. This study investigated the relationships of attitudinal factors with absenteeism and turnover intentions at a large healthcare organisation in the Bay of Plenty. A questionnaire completed by 407 employees had several measures such as job involvement, job satisfaction, organisational commitment (affective and continuance commitment), perceived organisational support, perceived supervisor support, work-to-family conflict, family-to-work conflict, team cohesion, regional identification and turnover intention. Absenteeism data were collected from personnel records.
The results indicated a probable association of job satisfaction, work-to-family conflict and perceived supervisor support with absenteeism, while turnover intention was associated with all predictors except continuance commitment. Perceived organisational support partially mediated the relationship between perceived supervisor support and turnover intention. No moderator effects were found for job involvement, perceived supervisor support and team cohesion on relationships between work-to-family conflict and affective commitment/job satisfaction and perceived organisational support and affective commitment respectively, however strong main effects were shown for job involvement and team cohesion.
The main finding is that organisations must understand how organisational and supervisor support increases job satisfaction and affective commitment and decreases work-to-family conflict, which lowers absenteeism and turnover intention. The detection of high levels of regional identification indicate the need to acknowledge this construct, particularly in relation to turnover intention.

year: 2008

title: Popoia te reo kia penapena: Nurture the language

authors: Berryman, Mere

subjects: Maori language

abstract: Research to develop a Māori language screening tool (Specialist Education Services, 2001), identified that students entering Māori Medium at five, could be classified into one of four Māori language competency, groups. Concurrently, teachers raised their need to identify the Māori language proficiency of five year olds entering Māori Medium so that more appropriate teaching strategies could be incorporated in preparation for literacy.
Accordingly, three Māori oral-language assessment tools, to help identify the Māori language competency of students entering Māori Medium settings at five years of age and provide formative information, were developed in response to this need. This paper details the development and trial of these tools.

text: Popoia te reo kia penapena: Nurture the language Research to develop a Māori language screening tool (Specialist Education Services, 2001), identified that students entering Māori Medium at five, could be classified into one of four Māori language competency, groups. Concurrently, teachers raised their need to identify the Māori language proficiency of five year olds entering Māori Medium so that more appropriate teaching strategies could be incorporated in preparation for literacy.
Accordingly, three Māori oral-language assessment tools, to help identify the Māori language competency of students entering Māori Medium settings at five years of age and provide formative information, were developed in response to this need. This paper details the development and trial of these tools.

year: 2009